Optical recording medium

ABSTRACT

An optical recording medium having at least a recording layer and a reflective layer on a substrate. The recording layer contains a dipyrromethene metal chelate compound obtained from a dipyrromethene compound represented by the general formula (1) and a metal ion: ##STR1## wherein R 1  to R 7  are defined in the specification.

BACKGROUND OF THE INVENTION

(i) Field of the Invention

The present invention relates to a dipyrromethene metal chelatecompound, and an optical recording medium in which said compound is usedand which is recordable and reproducible at a higher density as comparedwith a conventional technique.

(ii) Description of the Related Art

As a recordable-type optical recording medium which conforms to compactdisc (hereinafter abbreviated to "CD") standards, a CD-R (CD-Recordable)has been suggested and developed {e.g., Nikkei Electronics No. 465, p.107 (Jan. 23, 1989), and OPTICAL DATA STORAGE DIGEST SERIES, Vol. 1, p.45 (1989)}. As shown in FIG. 1, this CD-R comprises a transparent resinsubstrate 1, and a recording layer 2, a reflective layer 3 and aprotective layer 4 laminated in this order on the transparent resinsubstrate 1, and when the recording layer is irradiated with a highpower laser light, the recording layer gives rise to a physical or achemical change to record information in the form of pits. Theinformation in the form of the pits can be reproduced by irradiating aformed pit site with a low power laser light to detect the change of areflectance. For the record and the reproduction of the opticalrecording medium, a near infrared semiconductor laser having awavelength of 770 to 830 nm is usually used, and since the opticalrecording medium conforms to the standards of CDs such as Red Books andOrange Books, it has a feature that it is compatible with a CD playerand a CD-ROM player.

However, a record capacity of the above-mentioned conventional medium isabout 650 MB, and when the record of digital movies is taken intoconsideration, the capacity is insufficient. In recent years, with theremarkable increase of information volume, demands for the enhancementof the density and the capacity of the information recording medium haveincreased more and more.

Furthermore, the development of short wavelength semiconductor laserswhich can be utilized in an optical disc system has advanced, and redsemiconductor lasers having wavelengths of 680 nm, 650 nm and 635 nmhave been put to practical use {e.g., Nikkei Electronics No. 592, p. 65(Oct. 11, 1993)}. By shortening the wavelength of therecord/reproduction laser and increasing a numerical aperture of anobject lens, the size of beam spots can be reduced, which permits theformation of the high-density optical recording medium. In fact, theoptical recording medium having the large capacity in which the digitalmovies can be recorded for a long time has been developed by shorteningthe wavelength of the semiconductor laser, increasing the numericalaperture of the object lens, or using a data compression technique{e.g., Nikkei Electronics No. 589, p. 55 (Aug. 30, 1993), and No. 594,p. 169 (Nov. 8, 1993)}. Nowadays, there has been developed a digitalvideo disc (DVD) in which the digital movies are recorded for a periodof 2 or more hours. The DVD is a read only medium having a recordcapacity of 4.7 GB, and it has been desired to develop a recordableoptical disc suitable for this capacity.

In addition, a laser of 532 nm obtained by high-frequency conversion ofa YAG laser has also been put to practical use.

A blue/green semiconductor laser of 490 nm which is far shorter than 532nm has also be researched, but its practicable level has not beenattained {e.g., Applied Physics Letter, p. 1272-1274, Vol. 59 (1991),and Nikkei Electronics No. 552, p. 90 (Apr. 27, 1992)}.

In the case that the short wavelength laser is used, a linear recorddensity and a radial record density of the optical disc cantheoretically equally be increased, but under the existingcircumstances, it is difficult to increase the radial record density soas to be equal to the linear record density. Since the laser light isdiffracted and scattered by grooves or lands, the narrower a track pitchis, the smaller a signal detection light quantity is. It is limited fromthe viewpoint of a molding technique to narrow the track pitch whilemaintaining a groove depth sufficient to obtain a tracking signal.Moreover, if the grooves are deep and narrow, it is difficult to form auniform recording layer. In addition, edges of the grooves and the landsare not smooth but slightly rough, which causes noise. Such a badinfluence noticeably occurs at a position where the track pitch isnarrow to some extent. Taking these facts into consideration, it can besupposed that when the numerical aperture of the object lens at awavelength of 520 nm is 0.6, the limit of the groove pitch is about 0.5μm.

When a dye layer of the CD-R medium is irradiated with the laser lightto bring about a physical change or a chemical change and to therebyform the pits, an optical constant and a decomposition behavior of thedye are important factors for forming the good pits. If the lessdecomposable dye is used, sensitivity deteriorates, or if the noticeablydecomposable or the easily changeable dye is used, the interrelation ofthe pits and the radial land portions are largely affected, so that theformation of the reliable pits is difficult. In the conventional CD-Rmedium, a refractive index of the dye layer is low at a laser wavelengthwhich is used at a high record density, and an extinction coefficient isnot a suitable value, so that the reflectance is low and a sufficientmodulation amplitude cannot be obtained. In addition, the small pitsshould have been formed by a focused beam, but there are inconvenientlyformed the pits which are spread so largely as to have a large influenceon an environment, and a radial cross talk deteriorates. On thecontrary, in some cases, the pits are extremely small, so that thedesired modulation amplitude cannot be obtained. Therefore, it isnecessary to select the dye for the recording layer having the suitableoptical characteristics and decomposition behavior.

For example, Japanese Patent Application Laid-open No. 199045/1994 hassuggested an optical recording medium which is recordable andreproducible by a semiconductor laser having a wavelength of 680 nm. Ina recording layer of this medium, a cyanine dye is used, and theprobability of the high-density record and reproduction is exhibited,but there is not any description that the recording has actually beencarried out at the high density.

Furthermore, in U.S. Pat. Nos. 4,774,339, 4,916,711, 5,248,782,5,274,113 and 5,498,641, there have been disclosed chelate compounds ofdipyrromethenes and boron halides, but a description of the opticalrecording media using these compounds is not present.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a dipyrromethene metalchelate compound, and another object of the present invention is toprovide an optical recording medium suitable for a high-density recordwhich contains said compound and which is recordable and reproducible bya short wavelength laser having a wavelength of 520 to 690 nm.

The present inventors have intensively investigated to solve theabove-mentioned problems, and as a result, the present invention has.now been completed. That is to say, the present invention is as follows:

(1) An optical recording medium having at least a recording layer and areflective layer on a substrate, said recording layer containing adipyrromethene metal chelate compound obtained from a dipyrromethenecompound represented by the general formula (1) and a metal ion ##STR2##wherein R¹ to R⁷ are each independently a hydrogen atom, halogen atom,nitro group, cyano group, hydroxyl group, amino group, carboxyl group,sulfonic acid group, alkyl group having 1 to 20 carbon atoms,halogenoalkyl group having 1 to 20 carbon atoms, alkoxy group having 1to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms,alkoxyalkyl group having 2 to 20 carbon atoms, alkoxyalkoxy group having2 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, acylgroup having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20carbon atoms, alkylaminocarbonyl group having 2 to 20 carbon atoms,dialkylaminocarbonyl group having 3 to 20 carbon atoms,alkylcarbonylamino group having 2 to 20 carbon atoms,phenylcarbonylamino group having 7 to 20 carbon atoms,phenylaminocarbonyl group having 7 to 20 carbon atoms, phenoxycarbonylgroup having 7 to 20 carbon atoms, aralkyl group having 7 to 20 carbonatoms, aryl group having 6 to 20 carbon atoms, heteroaryl group having 5to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms,phenylthio group having 6 to 20 carbon atoms, alkenyloxycarbonyl grouphaving 3 to 20 carbon atoms, aralkyloxycarbonyl group having 8 to 20carbon atoms, alkoxycarbonylalkoxycarbonyl group having 4 to 20 carbonatoms, alkylcarbonylalkoxycarbonyl group having 4 to 20 carbon atoms,mono(hydroxyalkyl)aminocarbonyl group having 2 to 20 carbon atoms,di(hydroxyalkyl)aminocarbonyl group having 3 to 20 carbon atoms,mono(alkoxyalkyl)aminocarbonyl group having 3 to 20 carbon atoms ordi(alkoxyalkyl)aminocarbonyl group having 5 to 20 carbon atoms; R² andR³ and/or R⁵ and R⁶ may bond to each other to form an aromatic ringfused to a pyrrole ring; and the fused aromatic rings formed by thesegroups may be the same or different and are represented by formula (a):##STR3## wherein R⁸ to R¹¹ are each independently a hydrogen atom,halogen atom, nitro group, cyano group, hydroxyl group, amino group,carboxyl group, sulfonic acid group, alkyl group having 1 to 20 carbonatoms, halogenoalkyl group having 1 to 20 carbon atoms, alkoxy grouphaving 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms,alkoxyalkyl group having 2 to 20 carbon atoms, alkoxyalkoxy group having2 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, acylgroup having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20carbon atoms, alkylaminocarbonyl group having 2 to 20 carbon atoms,dialkylaminocarbonyl group having 3 to 20 carbon atoms,alkylcarbonylamino group having 2 to 20 carbon atoms,phenylcarbonylamino group having 7 to 20 carbon atoms,phenylaminocarbonyl group having 7 to 20 carbon atoms, phenoxycarbonylgroup having 7 to 20 carbon atoms, aralkyl group having 7 to 20 carbonatoms, aryl group having 6 to 20 carbon atoms, heteroaryl group having 5to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms,phenylthio group having 6 to 20 carbon atoms, alkenyloxycarbonyl grouphaving 3 to 20 carbon atoms, aralkyloxycarbonyl group having 8 to 20carbon atoms, alkoxycarbonylalkoxycarbonyl group having 4 to 20 carbonatoms, alkylcarbonylalkoxycarbonyl group having 4 to 20 carbon atoms,mono(hydroxyalkyl)aminocarbonyl group having 2 to 20 carbon atoms,di(hydroxyalkyl)aminocarbonyl group having 3 to 20 carbon atoms,mono(alkoxyalkyl)aminocarbonyl group having 3 to 20 carbon atoms ordi(alkoxyalkyl)aminocarbonyl group having 5 to 20 carbon atoms; and R¹⁰and R¹¹ may bond to each other to form an aromatic ring.

(2) The optical recording medium according to the above-mentionedparagraph (1) wherein the dipyrromethene metal chelate compound is acompound represented by the following general formula (2) ##STR4##wherein R¹ to R⁷ are as defined above; and M is a transition element.

(3) The optical recording medium according to the above-mentionedparagraph (1) wherein the dipyrromethene metal chelate compound is acompound represented by the following general formula (3) ##STR5##wherein R¹ to R⁷ are as defined above.

(4) The optical recording medium according to any one of theabove-mentioned paragraphs (1) to (3) which is recordable andreproducible by a laser light selected from the wavelength range of 520to 690 nm.

(5) The optical recording medium according to any one of theabove-mentioned paragraphs (1) to (3) wherein, at alaser wavelength, arefractive index of the recording layer is 1.8 or more, and anextinction coefficient of the recording layer is in the range of 0.04 to0.40.

(6) The optical recording medium according to any one of theabove-mentioned paragraphs (1) to (3) wherein a reflectance of a laserlight selected from the wavelength range of 520 to 690 nm is 20% ormore, as measured from the side of the substrate.

(7) A dipyrromethene metal chelate compound represented by the followinggeneral formula (4) ##STR6## wherein R¹ to R⁴ and R⁷ to R¹¹ are asdefined above; M is a transition element; but R² and R³ do not form anaromatic ring.

(8) A dipyrromethene metal chelate compound represented by the followinggeneral formula (5) ##STR7## wherein R¹ to R⁴ and R⁷ to R¹¹ are asdefined above; but R² and R³ do not form an aromatic ring.

According to the present invention, a dipyrromethene metal chelatecompound of a dipyrromethene compound and a metal ion is used as arecording layer, whereby a recordable type optical recording medium canbe provided which is very noticed as a high-density optical recordingmedium and which is recordable and reproducible by a laser having awavelength of 520 to 690 nm.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a sectional view illustrating a layer constitution of anoptical recording medium of a conventional technique and the presentinvention.

FIG. 2 is a sectional view illustrating a layer constitution of anoptical recording medium of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

In a dipyrromethene metal chelate compound of a dipyrromethene compoundrepresented by formula (1) and a metal ion according to the presentinvention, examples of R¹ to R¹¹ include a hydrogen atom; nitro group;cyano group; hydroxyl group; amino group; carboxyl group; sulfonic acidgroup; halogen atoms such as fluori ne, chlorine, bromine and iodine;

straight-chain, branched and cyclic alkyl groups having 1 to 20 carbonatoms such as a methyl group, ethyl group, n-propyl group, iso-propylgroup, n-butyl group, iso-butyl group, sec-butyl group, t-butyl group,n-pentyl group, iso-pentyl group, 2-methylbutyl group, 1-methylbutylgroup, neo-pentyl group, 1,2-dimethylpropyl group, 1,1-dimethylpropylgroup, cyclopentyl group, n-hexyl group, 4-methylpentyl group,3-methylpentyl group, 2-methylpentyl group, 1-methylpentyl group,3,3-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutylgroup, 2,2-dimethylbutyl group, 1,2-dimethylbutyl group,1,1-dimethylbutyl group, 3-ethylbutyl group, 2-ethylbutyl group,1-ethylbutyl group, 1,2,2-trimethylbutyl group, 1,1,2-trimethylbutylgroup, 1-ethyl-2-methylpropyl group, cyclohexyl group, n-heptyl group,2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group,5-methylhexyl group, 2,4-dimethylpentyl group, n-octyl group,2-ethylhexyl group, 2,5-dimethylhexyl group, 2,5,5-trimethylpentylgroup, 2,4-dimethylhexyl group, 2,2,4-trimethylpentyl group, n-octylgroup, 3,5,5-trimethylhexyl group, n-nonyl group, n-decyl group,4-ethyloctyl group, 4ethyl-4,5-methylhexyl group, n-undecyl group,n-dodecyl group, 1,3,5,7-tetraethyloctyl group, 4-butyloctyl group,6,6-diethyloctyl group, n-tridecyl group, 6-methyl-4-butyloctyl group,n-tetradecyl group, n-pentadecyl group, 3,5-dimethylheptyl group,2,6-dimethylheptyl group, 2,4-dimethylheptyl group,2,2,5,5-tetramethylhexyl group, 1-cyclopentyl-2,2-dimethylpropyl groupand 1-cyclohexyl-2,2-dimethylpropyl group;

halogenoalkyl groups having 1 to 20 carbon atoms such as a chloromethylgroup, dichloromethyl group, fluoromethyl group, trifluoromethyl group,pentafluoroethyl group and nonafluorobutyl group;

alkoxyalkyl groups having 2 to 20 carbon atoms such as a methoxyethylgroup, ethoxyethyl group, iso-propyloxyethyl group, 3-methoxypropylgroup and 2-methoxybutyl group;

alkoxy groups having 1 to 20 carbon atoms such as a methoxy group,ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group,iso-butoxy group, sec-butoxy group, t-butoxy group, n-pentoxy group,iso-pentoxy group, neo-pentoxy group, n-hexyloxy group and n-dodecyloxygroup;

alkenyl groups having 2 to 20 carbon atoms such as a vinyl group,propenyl group, 1-butenyl group, iso-butenyl group, 1-pentenyl group,2-pentenyl group, 2-methyl-1-butenyl group, 3-methyl-1-butenyl group,2-methyl-2-butenyl group, 2,2-dicyanovinyl group,2-cyano-2-methylcarboxyvinyl group and 2-cyano-2-methylsulfonevinylgroup;

alkoxyalkoxy groups having 2 to 20 carbon atoms such as a methoxyethoxygroup, ethoxyethoxy group, 3-methoxypropyloxy group and3-(iso-propyloxy)propyloxy group;

aryloxy groups having 6 to 20 carbon atoms such as a phenoxy group,2-methylphenoxy group, 4-methylphenoxy group, 4-t-butylphenoxy group,2-methoxyphenoxy group and 4-iso-propylphenoxy group;

acyl groups having 1 to 20 carbon atoms such as a formyl group, acetylgroup, ethylcarbonyl group, n-propylcarbonyl group, iso-propylcarbonylgroup, n-butylcarbonyl group, iso-butylcarbonyl group, sec-butylcarbonylgroup, t-butylcarbonyl group, n-pentylcarbonyl group, iso-pentylcarbonylgroup, neo-pentylcarbonyl group, 2-methylbutylcarbonyl group andnitrobenzylcarbonyl group;

alkoxycarbonyl groups having 2 to 20 carbon atoms such as amethoxycarbonyl group, ethoxycarbonyl group, isopropyloxycarbonyl groupand 2,4-dimethylbutyloxycarbonyl group;

alkylaminocarbonyl groups having 2 to 20 carbon atoms such as amethylaminocarbonyl group, ethylaminocarbonyl group,n-propylaminocarbonyl group, n-butylaminocarbonyl group andn-hexylaminocarbonyl group;

dialkylaminocarbonyl groups having 2 to 20 carbon atoms such as adimethylaminocarbonyl group, diethylaminocarbonyl group,di-n-propylaminocarbonyl group, di-n-butylaminocarbonyl group andN-methyl-N-cyclohexylaminocarbonyl group;

alkylcarbonylamino groups having 2 to 20 carbon atoms such as anacetylamino group, ethylcarbonylamino group and butylcarbonylaminogroup;

phenylaminocarbonyl groups having 7 to 20 carbon atoms such as aphenylaminocarbonyl group, 4-methylphenylaminocarbonyl group,2-methoxyphenylaminocarbonyl group and 4-n-propylphenylaminocarbonylgroup;

phenylcarbonylamino groups having 7 to 20 carbon atoms such as aphenylcarbonylamino group, 4-ethylphenylcarbonylamino group and3-butylphenylcarbonylamino group;

phenoxycarbonyl groups having 7 to 20 carbon atoms such as aphenoxycarbonyl group, 2-methylphenoxycarbonyl group,4-methoxyphenoxycarbonyl group and 4-t-butylphenoxycarbonyl group;

aralkyl groups having 7 to 20 carbon atoms such as a benzyl group,nitrobenzyl group, cyanobenzyl group, hydroxybenzyl group, methylbenzylgroup, dimethylbenzyl group, trimethylbenzyl group, dichlorobenzylgroup, methoxybenzyl group, ethoxybenzyl group, trifluoromethylbenzylgroup, naphthylmethyl group, nitronaphthylmethyl group,cyanonaphthylmethyl group, hydroxynaphthylmethyl group,methylnaphthylmethyl group and trif luoromethylnaphthylmethyl group;

aryl groups having 6 to 20 carbon atoms such as aphenyl group,nitrophenyl group, cyanophenyl group, hydroxyphenyl group, methylphenylgroup, dimethylphenyl group, trimethylphenyl group, dichlorophenylgroup, methoxyphenyl group, ethoxyphenyl group, trifluoromethylphenylgroup, N,N-dimethylaminophenyl group, naphthyl group, nitronaphthylgroup, cyanonaphthyl group, hydroxynaphthyl group, methylnaphthyl groupand trifluoromethylnaphthyl group;

heteroaryl groups having 5 to 20 carbon atoms such as a pyrrolyl group,thienyl group, furanyl group, oxazoyl group, isoxazoyl group, oxadiazoylgroup, imidazoyl group, benzoxazoyl group, benzothiazoyl group,benzimidazoyl group, benzofuranyl group and indoyl group;

alkylthio groups having 1 to 20 carbon atoms such as a methylthio group,ethylthio group, n-propylthio group, iso-propylthio group, n-butylthiogroup, iso-butylthio group, sec-butylthio group, t-butylthio group,n-pentylthio group, iso-pentylthio group, 2-methylbutylthio group,1-methylbutylthio group, neo-pentylthio group, 1,2-dimethylpropylthiogroup and 1,1-dimethylpropylthio group;

phenylthio groups having 6 to 20 carbon atoms such as a phenylthiogroup, 4-methylphenylthio group, 2-methoxyphenylthio group and4-t-butylphenylthio group;

alkenyloxycarbonyl groups having 3 to 20 carbon atoms such as anallyloxycarbonyl group and 2-butenoxycarbonyl group;

aralkyloxycarbonyl groups having 8 to 20 carbon atoms such as abenzyloxycarbonyl group and phenethyloxycarbonyl group;

alkoxycarbonylalkoxycarbonyl groups having 4 to 20 carbon atoms such asa methoxycarbonylmethoxycarbonyl group, ethoxycarbonylmethoxycarbonylgroup, n-propoxycarbonylmethoxycarbonyl group andisopropoxycarbonylmethoxycarbonyl group;

alkylcarbonylalkoxycarbonyl groups having 4 to 20 carbon atoms such as amethylcarbonylmethoxycarbonyl group and ethylcarbonylmethoxycarbonylgroup;

mono(hydroxyalkyl)aminocarbonyl groups having 2 to 20 carbon atoms suchas a hydroxyethylaminocarbonyl group, 2-hydroxypropylaminocarbonyl groupand 3-hydroxypropylaminocarbonyl group;

di(hydroxyalkyl)aminocarbonyl groups having 3 to 20 carbon atoms such asa di(hydroxyethyl)aminocarbonyl group, di(2-hydroxypropyl)aminocarbonylgroup and di(3-hydroxypropyl)aminocarbonyl group;

mono(alkoxyalkyl)aminocarbonyl groups having 3 to 20 carbon atoms suchas a methoxymethylaminocarbonyl group, methoxyethylaminocarbonyl group,ethoxymethylaminocarbonyl group, ethoxyethylaminocarbonyl group andpropoxyethylaminocarbonyl group; and

di(alkoxyalkyl)aminocarbonyl groups having 5 to 20 carbon atoms such asa di(methoxyethyl)aminocarbonyl group, di(ethoxymethyl)aminocarbonylgroup, di(ethoxyethyl)aminocarbonyl group anddi(propoxyethyl)aminocarbonyl group.

No particular restriction is put on a metal which can form the chel atecompound together with a dipyrromethene compound represented by formula(1), so long as it usually has an ability of forming the chelatecompound together with the dipyrromethene compound. Examples of such ametal include metals in the groups 8, 9 and 10 (the group VIII), thegroup 11 (the group Ib), the group 12 (the group IIb), the group 3 (thegroup IIIa), the group 4 (the group IVa), the group 5 (the group Va),the group 6 (the group VIa) and the group 7 (the group VIIa), andpreferable examples thereof include transition metals such as nickel,cobalt, iron, ruthenium, rhodium, palladium, copper, osmium, iridium,platinum and zinc.

No particular restriction is put on methods for preparing thedipyrromethene compound represented by formula (1) and thedipyrromethene metal chelate compound according to the presentinvention, but for example, they can be prepared in accordance withmethods described in Aust. J. Chem., Vol. 11, p. 1835-1845 (1965);Heteroatom Chemistry, Vol. 1, No. 5, p. 389 (1990); U.S. Pat. No.4,774,339; U.S. Pat. No. 5,433,896 and the like. Typically, they can beprepared through the following two-step reaction.

In a first step, a compound represented by formula (6) and a compoundrepresented by formula (7), or a compound represented by formula (8) anda compound represented by formula (9) are reacted in a suitable solventin the presence of an acid catalyst such as hydrobromic acid or hydrogenchloride to obtain a dipyrromethene compound represented by formula(10). Next, in the second step, the dipyrromethene compound representedby formula (10) is reacted with boron trifluoride, or an acetate or ahalide of a metal such as nickel, cobalt, iron, ruthenium, rhodium,palladium, copper, osmium, iridium, platinum or zinc to obtain a desireddipyrromethene metal chelate compound. ##STR8## wherein R¹ to R⁷ are asdefined above.

Table 1 shows typical examples of the metal chelate of thedipyrromethene compound represented by formula (1) according to thepresent invention together with substituents of the above-describedformulae (2) to (5) and the following formulae (11) and (12): ##STR9##

In Table 1, each compound number shows a corresponding formula numberand its serial number, for example, compound number 2-1 means the firstexample of the compound represented by formula (2).

                                      TABLE 1-1                                   __________________________________________________________________________    Compound                                                                            R.sup.1        R.sup.2                                                                            R.sup.3                                                                          R.sup.4       R.sup.5                                                                          R.sup.6                                                                            R.sup.7                                                                            M                     __________________________________________________________________________    2-1                                                                                 1 #STR10##     H    H                                                                                2 #STR11##    H  H    H    Zn                    2-2                                                                                 3 #STR12##     H    H                                                                                4 #STR13##    H  H    H    Zn                    2-3   CH.sub.3       C.sub.2 H.sub.5                                                                    CH.sub.3                                                                         H             CH.sub.3                                                                         C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           Zn                    2-4   CH.sub.3       C.sub.2 H.sub.5                                                                    CH.sub.3                                                                         4 #STR14##    CH.sub.3                                                                         C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           Zn                    2-5   CH.sub.3       C.sub.2 H.sub.5                                                                    CH.sub.3                                                                         H             CH.sub.3                                                                         C.sub.2 H.sub.5                                                                    CH.sub.3                                                                           Cu                    2-6                                                                                 5 #STR15##     H    H                                                                                6 #STR16##    H  H    H    Zn                    2-7   COOC.sub.2 H.sub.5                                                                           H    H                                                                                7 #STR17##    H  H    COOC.sub.2 H.sub.5                                                                 Cu                    2-8   CH.sub.3       COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                         H             CH.sub.3                                                                         COOC.sub.2 H.sub.5                                                                 CH.sub.3                                                                           Cu                    2-9   COOC.sub.2 H.sub.5                                                                           H    H  CN            H  H    H    Cu                     2-10 COOCH.sub.3    H    H  CN            H  H    COOCH.sub.3                                                                        Fe                    __________________________________________________________________________

                                      TABLE 1-2                                   __________________________________________________________________________    Compound                                                                            R.sup.1        R.sup.2 R.sup.3                                                                            R.sup.4                                     __________________________________________________________________________    2-11  CH.sub.3       COOCH.sub.3                                                                           CH.sub.3                                                                           8 #STR18##                                  2-12  CH.sub.3       CO.sub.2 C.sub.2 H.sub.5                                                              CH.sub.3                                                                           9 #STR19##                                  2-13  Br             C.sub.2 H.sub.5                                                                       CH.sub.3                                                                           H                                           2-14  CH.sub.3       --(CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                  CH.sub.3                                                                           H                                           2-15  --CH.sub.2 OCH.sub.3                                                                         C.sub.2 H.sub.5                                                                       CH.sub.3                                                                           H                                           2-16                                                                                3 #STR20##     H       H                                                                                  4 #STR21##                                  2-17  CH.sub.3       CO.sub.2 C.sub.2 H.sub.5                                                              CH.sub.3                                                                           0 #STR22##                                  2-18  Br             CH.sub.3                                                                              CO.sub.2 C.sub.2 H.sub.5                                                           H                                           2-19  OCH.sub.3      CH.sub.3                                                                              C.sub.2 H.sub.5                                                                    H                                           2-20                                                                                1 #STR23##     H       OCH.sub.3                                                                          H                                           2-21  CH.sub.3       H       CH.sub.3                                                                           H                                           2-22  CO.sub.2 C.sub.2 H.sub.5                                                                     Cl      Cl   H                                           2-23  CH.sub.3       --(CH.sub.2).sub.2 CH.sub.3                                                           H    --(CH.sub.2).sub.3 CH.sub.3                 __________________________________________________________________________               Compound                                                                            R.sup.5 R.sup.6                                                                            R.sup.7        M                                __________________________________________________________________________               2-11  CH.sub.3                                                                              COOCH.sub.3                                                                        CH.sub.3       Ni                                          2-12  CH.sub.3                                                                              CO.sub.2 C.sub.2 H.sub.5                                                           CH.sub.3       Ni                                          2-13  C.sub.2 H.sub.5                                                                       CH.sub.3                                                                           Br             Co                                          2-14  --(CH.sub.2).sub.2 CO.sub.2 CH.sub.3                                                  CH.sub.3                                                                           Br             Co                                          2-15  CH.sub.3                                                                              C.sub.2 H.sub.5                                                                    --CH.sub.2 OCH.sub.3                                                                         Ni                                          2-16  H       H                                                                                  3 #STR24##     Zn                                          2-17  CH.sub.3                                                                              CO.sub.2 C.sub.2 H.sub.5                                                           CH.sub.3       Cu                                          2-18  CO.sub.2 C.sub.2 H.sub.5                                                              CH.sub.3                                                                           Br             Pd                                          2-19  H       H    H              Zn                                          2-20  H       H    --(CH.sub.2).sub.2 CH.sub.3                                                                  Zn                                          2-21  CH.sub.3                                                                              H    CH.sub.3       Mn                                          2-22  Cl      Cl   CO.sub.2 OC.sub.2 H.sub.5                                                                    Co                                          2-23  CO.sub.2 C.sub.2 H.sub.5                                                              CH.sub.3                                                                           Br             Cu                               __________________________________________________________________________

                                      TABLE 1-3                                   __________________________________________________________________________    Compound                                                                            R.sup.1 R.sup.2         R.sup.3                                                                           R.sup.4                                     __________________________________________________________________________    3-1   CH.sub.3                                                                              H               CH.sub.3                                                                          CH.sub.3                                    3-2   CH.sub.3                                                                              C.sub.2 H.sub.5 CH.sub.3                                                                          8 #STR25##                                  3-3   CH.sub.3                                                                              CH═CH.sub.2 CH.sub.3                                                                          CH.sub.3                                    3-4   CH.sub.3                                                                              COCH.sub.3      CH.sub.3                                                                          CH.sub.3                                    3-5   CH.sub.3                                                                              CO.sub.2 C.sub.2 H.sub.5                                                                      CH.sub.3                                                                          CN                                          3-6   CH.sub.3                                                                              C.sub.2 H.sub.5 CH.sub.3                                                                          CH.sub.2 OCOCH.sub.3                        3-7   H       O(CH.sub.2).sub.2 OCH(CH.sub.3).sub.2                                                         CH.sub.3                                                                          H                                           3-8   CH.sub.3                                                                              2 #STR26##      H   H                                           3-9   CO.sub.2 C.sub.2 H.sub.5                                                              CH.sub.3        COCH.sub.3                                                                        H                                            3-10                                                                               3 #STR27##                                                                            H               H   H                                            3-11 CH.sub.3                                                                              SO.sub.3 H      CH.sub.3                                                                          CH.sub.3                                     3-12 CH.sub.3                                                                              CONHCH(CH.sub.3).sub.2                                                                        C.sub.2 H.sub.5                                                                   H                                            3-13 CO.sub.2 C.sub.2 H.sub.5                                                              NHCOC.sub.2 H.sub.5                                                                           CH.sub.3                                                                          H                                            3-14 CH.sub.3                                                                              4 #STR28##      CH.sub.3                                                                          CH.sub.3                                     3-15 CH.sub.3                                                                              5 #STR29##      CH.sub.3                                                                          CH.sub.3                                     3-16 CO.sub.2 C.sub.2 H.sub.5                                                              SCH(CH.sub.3).sub.2                                                                           CH.sub.3                                                                          CH.sub.3                                     3-17 COOH                                                                                  6 #STR30##      CH.sub.3                                                                          H                                           __________________________________________________________________________                 Compound                                                                            R.sup.5                                                                           R.sup.6         R.sup.7                                __________________________________________________________________________                 3-1   CH.sub.3                                                                          H               CH.sub.3                                            3-2   CH.sub.3                                                                          C.sub.2 H.sub.5 CH.sub.3                                            3-3   CH.sub.3                                                                          CH═CH.sub.2 CH.sub.3                                            3-4   CH.sub.3                                                                          COCH.sub.3      CH.sub.3                                            3-5   CH.sub.3                                                                          CO.sub.2 C.sub.2 H.sub.5                                                                      CH.sub.3                                            3-6   CH.sub.3                                                                          C.sub.2 H.sub.5 CH.sub.3                                            3-7   CH.sub.3                                                                          O(CH.sub.2).sub.2 OCH(CH.sub.3).sub.2                                                         H                                                   3-8   H                                                                                 2 #STR31##      CH.sub.3                                            3-9   COCH.sub.3                                                                        CH.sub.3        CO.sub.2 C.sub.2 H.sub.5                             3-10 CH.sub.3                                                                          H               CH.sub.3                                             3-11 CH.sub.3                                                                          SO.sub.3 H      CH.sub.3                                             3-12 C.sub.2 H.sub.5                                                                   CO.sub.2 CH.sub.3                                                                             CH.sub.3                                             3-13 CH.sub.3                                                                          NHCOC.sub.2 H.sub.5                                                                           CO.sub.2 C.sub.2 H.sub.5                             3-14 CH.sub.3                                                                          4 #STR32##      CH.sub.3                                             3-15 CH.sub.3                                                                          5 #STR33##      CH.sub.3                                             3-16 CH.sub.3                                                                          SCH(CH.sub.3).sub.2                                                                           CO.sub.2 C.sub.2 H.sub.5                             3-17 CH.sub.3                                                                          6 #STR34##      COOH                                   __________________________________________________________________________

                                      TABLE 1-4                                   __________________________________________________________________________    Compound                                                                            R.sup.1                                                                            R.sup.2                                                                           R.sup.3                                                                            R.sup.4                                                                         R.sup.8                                                                         R.sup.9                                                                         R.sup.10                                                                         R.sup.11                                                                         R.sup.7         M                             __________________________________________________________________________    4-1   CH.sub.3                                                                           H   CH.sub.3                                                                           H H H H  H                                                                                8 #STR35##      Co                            4-2   CH.sub.3                                                                           H   CH.sub.3                                                                           H H H H  H                                                                                7 #STR36##      Co                            4-3   CH.sub.3                                                                           H   CH.sub.3                                                                           H H H H  H                                                                                8 #STR37##      Zn                            4-4   CH.sub.3                                                                           H   CH.sub.3                                                                           H H H H  H                                                                                6 #STR38##      Co                            4-5   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   CH.sub.3                                                                           H H H H  H                                                                                8 #STR39##      Co                            4-6   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   CH.sub.3                                                                           H H H H  H                                                                                8 #STR40##      Zn                            4-7   CH.sub.3                                                                           H   CH.sub.3                                                                           H H H H  H                                                                                6 #STR41##      Zn                            4-8   CH.sub.3                                                                           H   CH.sub.3                                                                           CN                                                                              H H H  H                                                                                6 #STR42##      Cu                            4-9   CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                    H H H H  H  Br              Cu                             4-10 CO.sub.2 C.sub.2 H.sub.5                                                           C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                    H H H H  H  SC.sub.2 H.sub.5                                                                              Co                             4-11 CO.sub.2 C.sub.2 H.sub.5                                                           C.sub.2 H.sub.5                                                                   C.sub.2 H.sub.5                                                                    H F F F  F                                                                                8 #STR43##      Fe                             4-12 CO.sub.2 C.sub.2 H.sub.6                                                           n-C.sub.6 H.sub.17                                                                C.sub.2 H.sub.5                                                                    H Br                                                                              Br                                                                              Br Br                                                                               6 #STR44##      Zn                             4-13 CO.sub.2 C.sub.2 H.sub.6                                                           n-C.sub.6 H.sub.13                                                                CO.sub.2 C.sub.2 H.sub.5                                                           H H H H  H                                                                                9 #STR45##      Zn                            __________________________________________________________________________

    TABLE 1-5      - Compound R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.8 R.sup.9 R.sup.10     R.sup.11 R.sup.7 M      4-14 CH.sub.3 C.sub.2      H.sub.5     ##STR46##     8  H H OCH.sub.3 OCH.sub.3 H      ##STR47##     2  Ni     4-15 CH.sub.3      ##STR48##     8      ##STR49##     8  H H H H H CH.sub.3 Co     4-16 CH.sub.3 COCH.sub.3      ##STR50##     8  CN H H H H C.sub.2      H.sub.5 Ni                          4-17 CH.sub.3 (CH.sub.2).sub.2 CO.sub.2 CH.sub.3     CH.sub.3 CN H OC.sub.2 H.sub.5 OC.sub.2      H.sub.5 H     ##STR51##     8  Cu     4-18      ##STR52##     3  H H CN H OCH.sub.3 OCH.sub.3 H      ##STR53##     8  Ni     4-19 CH.sub.3 CO.sub.2 CH.sub.2 CO.sub.2 CH.sub.3 CH.sub.3 H H H H H Cl     Zn     4-20 Br CH.sub.3 CO.sub.2 C.sub.2      H.sub.5 H OCH.sub.3 OCH.sub.3 OCH.sub.3 OCH.sub.3      ##STR54##     8  Fe     4-21 OCH.sub.3 CH.sub.3 C.sub.2      H.sub.5 H H H Cl H     ##STR55##     8  Fe     4-22      ##STR56##     1  H OCH.sub.3 H H H H H      ##STR57##     6  Cu     4-23 CO.sub.2 C.sub.2      H.sub.5 Cl Cl CN H H     ##STR58##     6  H H Ni     4-24 CH.sub.3 n-C.sub.4      H.sub.9 H CN H     ##STR59##     8      ##STR60##     8  H H Co     4-25 CH.sub.3 O(CH.sub.2).sub.3 OC(CH.sub.3).sub.3 CH.sub.3 H H H     SCH.sub.3 H      ##STR61##     8  Co

                                      TABLE 1-6                                   __________________________________________________________________________    Compound                                                                            R.sup.1 R.sup.2         R.sup.3                                                                            R.sup.4                                                                         R.sup.8                                                                         R.sup.9                                __________________________________________________________________________    4-26  CH.sub.3                                                                              2 #STR62##      H    H H OCH.sub.3                              4-27  CO.sub.2 C.sub.2 H.sub.5                                                              CH.sub.3        CO.sub.2 CH.sub.3                                                                  H H                                                                               8 #STR63##                             4-28                                                                                3 #STR64##                                                                            SO.sub.3 H      H    CN                                                                              H H                                      4-29  CH.sub.3                                                                              SO.sub.3 H      CH.sub.3                                                                           H H H                                      4-30  CH.sub.3                                                                              CONHCH(CH.sub.3).sub.2                                                                        H    H H H                                      4-31  CO.sub.2 C.sub.2 H.sub.5                                                              NHCOC.sub.2 H.sub.5                                                                           CH.sub.3                                                                           H H H                                      4-32  CH.sub.3                                                                              4 #STR65##      CH.sub.3                                                                           H H H                                      4-33  CH.sub.3                                                                              5 #STR66##      CH.sub.3                                                                           CN                                                                              H OC.sub.2 H.sub.5                       4-34  CO.sub.2 C.sub.2 H.sub.5                                                              SC(CH.sub.3).sub.3                                                                            CH.sub.3                                                                           CN                                                                              H H                                      4-35  CO.sub.2 H                                                                            6 #STR67##      CH.sub.3                                                                           H F F                                      4-35  CH.sub.3                                                                              NO.sub.2        CH.sub.3                                                                           H H H                                      4-37  CH.sub.3                                                                              CN              H    H H H                                      4-38  OH      CONHCH.sub.2 OCH.sub.3                                                                        CH.sub.3                                                                           CN                                                                              H H                                      __________________________________________________________________________                Compound                                                                            R.sup.10  R.sup.11                                                                         R.sup.7         M                              __________________________________________________________________________                4-26  OCH.sub.3 H  CH.sub.3        Zn                                         4-27                                                                                8 #STR68##                                                                              H  CO.sub.2 CH.sub.3                                                                             Co                                         4-28  Cl        H  CO.sub.2 CH.sub.3                                                                             Zn                                         4-29  H         H  OC.sub.2 H.sub.5                                                                              Zn                                         4-30  H         H  CN              Pd                                         4-31  H         H  NHC.sub.2 H.sub.5                                                                             Co                                         4-32  H         H                                                                                8 #STR69##      Pd                                         4-33  OC.sub.2 H.sub.5                                                                        H  N(CH.sub.3).sub.2                                                                             Mn                                         4-34  H         H                                                                                8 #STR70##      Ni                                         4-35  F         F                                                                                2 #STR71##      Co                                         4-35  H         H                                                                                0 #STR72##      Zn                                         4-37  H         H                                                                                1 #STR73##      Mn                                         4-38  H         H                                                                                2 #STR74##      Ni                             __________________________________________________________________________

    TABLE 1-7      - Compound R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.8 R.sup.9 R.sup.10     R.sup.11 R.sup.7 M      4-39 NH.sub.2 C.sub.2      H.sub.5 CH.sub.3 CN H H Cl H                 ##STR75##     0  Mn     4-40 C.sub.2 F.sub.5 CON(CH.sub.2 OCH.sub.3).sub.2 C.sub.2 H.sub.5 H H H     H H CO.sub.2 C.sub.2      H.sub.5 Co                                           4-41 CH.sub.2     OCH.sub.3 C.sub.2 H.sub.5 CH.sub.3 H H H H H CO.sub.2 C.sub.2 H.sub.5 Fe     4-42      ##STR76##     3  C.sub.2      H.sub.5 CH.sub.3 H Cl Cl Cl Cl                 ##STR77##     8  Co     4-43 CH.sub.3 CO.sub.2 CH.sub.2      COCH.sub.3 H H H H H H Br Fe                                    4-44 CH.sub.3      ##STR78##     4  CH.sub.3 CN H H H H C(CH.sub.3).sub.3 Fe     4-45 H      ##STR79##     5  H H H OCH.sub.3 OCH.sub.3 H CH.sub.3 Cu     4-46 H CH═CH.sub.2 H H H H H H      ##STR80##     8  Ni     4-47 CH.sub.3 C.sub.2 H.sub.5 C.sub.2      H.sub.5 H H H H H                 ##STR81##     6  Cu     4-48 CH.sub.3 C.sub.2      H.sub.5 CH.sub.3 H H H H H                 ##STR82##     6  Co     4-49 CH.sub.3 CH.sub.3 OCH.sub.3 H H H H H      ##STR83##     8  Co     4-50 CH.sub.3 C.sub.2      H.sub.5 CH.sub.3 H H H H H                 ##STR84##     7  Zn     4-51      ##STR85##     8  H      ##STR86##     8  H H H H H      ##STR87##     6  Cu

                                      TABLE 1-8                                   __________________________________________________________________________                3                                                                 Compound                                                                            R.sup.1                                                                          R.sup.2   R.sup.3   R.sup.4                                                                         R.sup.8                                                                         R.sup.9                                                                         R.sup.10                                                                         R.sup.11                                                                         R.sup.7                              __________________________________________________________________________    5-1   CH.sub.3                                                                         H         CH.sub.3  H H H H  H                                                                                8 #STR88##                           5-2   CH.sub.3                                                                         H         CH.sub.3  H H H H  H                                                                                7 #STR89##                           5-3   CH.sub.3                                                                         H         CH.sub.3  H H H H  H                                                                                6 #STR90##                           5-4   CH.sub.3                                                                         C.sub.2 H.sub.5                                                                         CH.sub.3  H H H H  H                                                                                8 #STR91##                           5-5   CH.sub.3                                                                         C.sub.2 H.sub.5                                                                         CH.sub.3  CN                                                                              H H H  H  Cl                                   5-6   CH.sub.3                                                                         C.sub.2 H.sub.5                                                                         C.sub.2 H.sub.5                                                                         H H H H  H  Br                                   5-7   CH.sub.3                                                                         C.sub.2 H.sub.5                                                                         8 #STR92##                                                                              H H H H  H                                                                                8 #STR93##                           5-8   CH.sub.3                                                                         8 #STR94##                                                                              8 #STR95##                                                                              H H H H  H  SCH.sub.3                            5-9   CH.sub.3                                                                         8 #STR96##                                                                              8 #STR97##                                                                              H H H H  H  Cl                                    5-10 CH.sub.3                                                                         C.sub.2 H.sub.5                                                                         8 #STR98##                                                                              H H H H  H  SC.sub.2 H.sub.5                      5-11 CH.sub.3                                                                         COCH.sub.3                                                                              8 #STR99##                                                                              CN                                                                              H F H  H                                                                                7 #STR100##                           5-12 CH.sub.3                                                                         COCH.sub.3                                                                              8 #STR101##                                                                             H H H H  H                                                                                8 #STR102##                          __________________________________________________________________________

                                      TABLE 1-9                                   __________________________________________________________________________    Compound                                                                            R.sup.1        R.sup.2      R.sup.3                                                                            R.sup.4                                                                         R.sup.8                                                                         R.sup.9                            __________________________________________________________________________    5-13                                                                                3 #STR103##    H            H    H H H                                  5-14  CH.sub.3       CO.sub.2 C.sub.2 H.sub.5                                                                   CH.sub.3                                                                           H H H                                  5-15  CH.sub.3       CO.sub.2 C.sub.2 H.sub.5                                                                   CH.sub.3                                                                           H H H                                  5-16  Br             CH.sub.3     CO.sub.2 C.sub.2 H.sub.5                                                           CN                                                                              H H                                  5-17  OCH.sub.3      CH.sub.3     C.sub.2 H.sub.5                                                                    H H H                                  5-18  OCH.sub.3      CH.sub.3     C.sub.2 H.sub.5                                                                    CN                                                                              F F                                  5-19                                                                                1 #STR104##    H            OCH.sub.3                                                                          H H H                                  5-20  CO.sub.2 C.sub.2 H.sub.5                                                                     Cl           Cl   H H H                                  5-21  CH.sub.3                                                                                     2 #STR105##  H    H H H                                  5-22  CH.sub.3                                                                                     2 #STR106##  H    H H OCH.sub.3                          5-23  CH.sub.3       CONHCH(CH.sub.3).sub.2 CH.sub.3                                                            H    H Br                                                                              Br                                 5-24  CO.sub.2 C.sub.2 H.sub.5                                                                     NHCOC.sub.2 H.sub.5                                                                        CH.sub.3                                                                           H H OC.sub.2 H.sub.5                   __________________________________________________________________________             Compound                                                                            R.sup.10        R.sup.11                                                                         R.sup.7                                     __________________________________________________________________________             5-13  Cl              H                                                                                8 #STR107##                                          5-14  Cl              H                                                                                2 #STR108##                                          5-15  H               H  CH.sub.3                                             5-16  SCH.sub.3       H                                                                                8 #STR109##                                          5-17                                                                                6 #STR110##     H  H                                                    5-18  F               F  H                                                    5-19  H               H                                                                                9 #STR111##                                          5-20  H               H                                                                                2 #STR112##                                          5-21  H               H                                                                                9 #STR113##                                          5-22  OCH.sub.3       H  CH.sub.3                                             5-23  Br              Br Br                                                   5-24  OC.sub.2 H.sub.5                                                                              H  CH.sub.3                                    __________________________________________________________________________

    TABLE 1-10      - Compound R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.8 R.sup.9 R.sup.10     R.sup.11 R.sup.7      5-25 CO.sub.2 C.sub.2      H.sub.5              ##STR114##     8  CH.sub.3 CN SC.sub.2 H.sub.5 SC.sub.2 H.sub.5 SC.sub.2 H.sub.5     SC.sub.2      H.sub.5 OH            5-26 CH.sub.3      ##STR115##     9  CH.sub.3 CN H      ##STR116##     8      ##STR117##     8  H      ##STR118##     8     5-27 CO.sub.2 C.sub.2 H.sub.5 SC(CH.sub.3).sub.3 CH.sub.3 H OCH.sub.3     OCH.sub.3 OCH.sub.3 OCH.sub.3      ##STR119##     8     5-28 C.sub.2 H.sub.5 CO.sub.2 CH═CH.sub.2 C.sub.2 H.sub.5 H H H H H     CO.sub.2      CH.sub.3                                                         5-29     CH.sub.3 CON(C.sub.2 H.sub.5).sub.2 C.sub.2 H.sub.5 H H H H H OC.sub.2     H.sub.5      5-30 CON(CH.sub.2 OH).sub.2 n-C.sub.8 H.sub.17 C.sub.2 H.sub.5 H H H H     H CN     5-31 CO.sub.2 C.sub.2      H.sub.5              ##STR120##     0  CO.sub.2 C.sub.2      H.sub.5 CN H H H H NHCH.sub.3                        5-32 CH.sub.3 NO.sub.2 CH.sub.3 H H OCH.sub.3     OCH.sub.3 H NHCH.sub.3      5-33 NH.sub.2 C.sub.2      H.sub.5 CH.sub.3 H F F F F NO.sub.2                           5-34 CONHCH.sub.2 OH C.sub.2 H.sub.5 C.sub.2     H.sub.5 H H H CO.sub.2      H H              ##STR121##     6     5-35 H      ##STR122##     1  H H H H Cl H OCH.sub.2 OC.sub.2      H.sub.5                                       5-36 CH.sub.3 CH═CH.sub.2 CH.sub.3     H H H      ##STR123##     6  H      ##STR124##     8     5-37 CH.sub.3 C.sub.2      H.sub.5 CH.sub.3 H H H H H              ##STR125##     6

                                      TABLE 1-11                                  __________________________________________________________________________             .                                                                    Compound                                                                            R.sup.1      R.sup.11                                                                             R.sup.10                                                                           R.sup.9                                                                         R.sup.8                                                                         R.sup.4                                                                         R.sup.8 '                                                                       R.sup.9 '                              __________________________________________________________________________    11-1  C(CH.sub.3).sub.3                                                                          H      H    H H H H H                                      11-2                                                                                8 #STR126##  --CH═CH--CH═CH--                                                                  H H H H H                                      11-3  C(CH.sub.3).sub.3                                                                          C(CH.sub.3).sub.3                                                                    H    H H H H H                                      11-4                                                                                7 #STR127##  --CH═CH--CH═CH--                                                                  H H H H H                                      11-5  C(CH.sub.3).sub.3                                                                          H      H    H H H H H                                      11-6                                                                                8 #STR128##  --CH═CH--CH═CH--                                                                  H H H H H                                      11-7  C(CH.sub.3).sub.3                                                                          C(CH.sub.3).sub.3                                                                    H    H H H H H                                      11-8                                                                                7 #STR129##  --CH═CH--CH═CH--                                                                  H H H H H                                      11-9  C(CH.sub.3).sub.3                                                                          H      H    H H H H H                                       11-10                                                                              8 #STR130##  --CH═CH--CH═CH--                                                                  H H H H H                                      __________________________________________________________________________            Compound                                                                            R.sup.10 '                                                                         R.sup.11 '                                                                           R.sup.7      M                                      __________________________________________________________________________            11-1  H    H      C(CH.sub.3).sub.3                                                                          Zn                                             11-2  --CH═CH--CH═CH--                                                                  8 #STR131##  Zn                                             11-3  H    OCH.sub.3                                                                            C(CH.sub.3).sub.3                                                                          Zn                                             11-4  --CH═CH--CH═CH--                                                                  7 #STR132##  Zn                                             11-5  H    H      C(CH.sub.3).sub.3                                                                          Cu                                             11-6  --CH═CH--CH═CH--                                                                  8 #STR133##  Cu                                             11-7  H    OCH.sub.3                                                                            C(CH.sub.3).sub.3                                                                          Fe                                             11-8  --CH═CH--CH═CH--                                                                  7 #STR134##  Co                                             11-9  H    H      C(CH.sub.3).sub.3                                                                          Ni                                              11-10                                                                              --CH═CH--CH═CH--                                                                  8 #STR135##  Pd                                     __________________________________________________________________________

                                      TABLE 1-12                                  __________________________________________________________________________    Compound                                                                            R.sup.1         R.sup.11                                                                              R.sup.10     R.sup.9                                                                              R.sup.8                                                                         R.sup.4                                                                         R.sup.8 '               __________________________________________________________________________    12-1  C(CH.sub.3).sub.3                                                                             H       H            H      H H H                       12-2                                                                                8 #STR136##     --CH═CH--CH 'CH--                                                                              H      H H H                       12-3  C(CH.sub.3).sub.3                                                                             C(CH.sub.3).sub.3                                                                     H            H      H H H                       12-4                                                                                7 #STR137##     --CH═CH--CH═CH--                                                                           H      H H H                       12-5  C(CH.sub.3).sub.3                                                                             OCH.sub.3                                                                             H            CH.sub.2 OCOCH.sub.3                                                                 H H H                       12-6  CH.sub.3        CONHCH(CH.sub.3).sub.2                                                                H            Br     H H H                       12-7  CH.sub.3        SCH(CH.sub.3).sub.2                                                                   H            NHCOC.sub.2 H.sub.5                                                                  H H H                       12-8                                                                                6 #STR138##     --CH═CH--CH═CH--                                                                           COCH.sub.3                                                                           H H H                       12-9  C(CH.sub.3).sub.3                                                                             C(CH.sub.3).sub.3                                                                     2 #STR139##  COOH   H H H                        12-10                                                                              C(CH.sub.3).sub.3                                                                             1 #STR140##                                                                           H            CH.sub.2 OCOCH.sub.3                                                                 H H H                       __________________________________________________________________________    Compound    R.sup.9 '                                                                            R.sup.10 '   R.sup.11 '                                                                            R.sup.7                               __________________________________________________________________________    12-1        H      H            H       C(CH.sub.3).sub.3                     12-2        H      --CH═CH--CH═CH--                                                                           8 #STR141##                           12-3        H      H            OCH.sub.3                                                                             C(CH.sub.3).sub.3                     12-4        H      --CH═CH--CH═CH--                                                                           7 #STR142##                           12-5        CH.sub.2 OCOCH.sub.3                                                                 H            OCH.sub.3                                                                             C(CH.sub.3).sub.3                     12-6        Br     H            CONHCH(CH.sub.3).sub.2                                                                CH.sub.3                              12-7        NHCOC.sub.2 H.sub.5                                                                  H            SCH(CH.sub.3).sub.2                                                                   CH.sub.3                              12-8        COCH.sub.3                                                                           --CH═CH--CH═CH--                                                                           6 #STR143##                           12-9        COOH                                                                                 2 #STR144##  C(CH.sub.3).sub.3                                                                     C(CH.sub.3).sub.3                      12-10      CH.sub.2 OCOCH.sub.3                                                                 H                                                                                          1 #STR145##                                                                           C(CH.sub.3).sub.3                     __________________________________________________________________________

The constitution of the present invention will be described in detail asfollows.

The optical recording medium denotes both of an optical ROM medium forreproduction alone in which information is beforehand recorded, and anoptical recording medium by which the information can be recorded andthen reproduced. However, reference will here be made to the latteroptical recording medium as a suitable example by which the informationcan be recorded and reproduced, particularly the optical recordingmedium having a recording layer and a reflective layer on a substrate.As shown in FIG. 1, this optical recording medium has a four-layerstructure in which the substrate, the recording layer, the reflectivelayer and a protective layer are laminated in turn, or such a laminatedstructure as shown in FIG. 2. That is to say, a recording layer 2' isformed on a substrate 1', and a reflective layer 3' is closely formedthereon. Furthermore, a substrate 5' is stuck on the reflective layer 3'via an adhesive layer 4'. However, another layer may be formed under oron the recording layer 2', and still another layer may be formed on thereflective layer.

A material for the substrate should fundamentally be transparent for awavelength of a record light and a reproduction light. Utilizableexamples of such a material include polymeric materials such aspolycarbonate resins, vinyl chloride resins, acrylic resins such aspolymethyl methacrylate, polystyrene resins and epoxy resins as well asinorganic materials such as glass. The substrate material is molded intoa disc substrate by injection molding or the like. If necessary, guidegrooves or pits may be formed on the surface of the substrate. Suchguide grooves or pits are preferably formed at the time of the moldingof the substrate, but they can also be formed by the use of anultraviolet curing resin layer on the substrate. In the case that theoptical recording medium is used in the form of a CD, the substrate is adisc having a thickness of about 1.2 mm and a diameter of about 80 to120 mm, and having a hole of about 15 mm in diameter in its center.

In the present invention, the recording layer is formed on thesubstrate, and the recording layer of the present invention contains thechelate compound of the dipyrromethene compound represented by thegeneral formula (1) and the metal ion. The maximum absorption λ_(max) ofthe chelate compound is present in 450 to 630 nm. In particular, therecording layer is required to have an optical constant suitable for arecord and reproduction laser wavelength selected in the range of 520 to690 nm.

The optical constant is represented by a complex index of refraction(n+iκ) wherein n and κ are coefficients of a real number and animaginary number, respectively, and herein, n and κ mean an ordinaryrefractive index and an extinction coefficient, respectively. Ingeneral, an organic dye has a feature that the refractive index n andthe extinction coefficient κ largely change to a wavelength λ. In viewof this feature, the organic dye having the preferable optical constantsuitable for the desired laser wavelength should be selected to form therecording layer, whereby the medium having a high reflectance and a goodsensitivity can be obtained.

According to the present invention, the optical constant necessary forthe recording layer is such that, at the above-mentioned wavelength ofthe laser light, n is 1.8 or more and κ is in the range of 0.04 to 0.40,and preferably n is 2.0 or more and κ is in the range of 0.04 to 0.20.If n is less than 1.8, the reflectance and the signal modulationamplitude necessary for a correct signal read may not be obtained, andif κ is more than 0.40, the reflectance is low, so that a goodregenerative signal may not be obtained and in addition, the signal isliable to change by a regenerative light. Hence, the recording layerhaving such an extinction coefficient κ may be not practical. In view ofthis feature, the organic dye having the preferable optical constantsuitable for the desired laser wavelength should be selected to form therecording layer, whereby the medium having a high reflectance and a goodsensitivity can be obtained. The chelate compound of the dipyrromethenecompound represented by the general formula (1) with a metal of thepresent invention has a higher absorption coefficient as compared with aconventional organic dye and can optionally select an absorptionwavelength section by the choice of a substituent. Therefore, it is anextremely useful compound which can satisfy the optical constant (n is1.8 or more and κ is in the range of 0.04 to 0.40, and preferably n is2.0 or more and κ is in the range of 0.04 to 0.20) necessary for therecording layer at the above-mentioned wavelength of the laser light.

In the case that the optical recording medium of the present inventionis reproduced by the laser light selected in the range of 520 to 690 nm,the reproduction is basically possible when the reflectance is 20% ormore, but it is preferred that the reflectance is 30% or more.

Furthermore, for the improvement of record characteristics and the like,the recording layer may be mixed with a dye, other than mentioned above,having a maximum absorption in the wavelength range of 450 to 630 nm anda large refractive index in the range of 520 to 690 nm. Typical examplesof such a dye include cyanine dyes, squalirium dyes, naphthoquinonedyes, anthraquinone dyes, porphyrin dyes, tetrapyraporphyrazine dyes,indophenol dyes, pyrylium dyes, thiopyrylium dyes, azulenium dyes,triphenylmethane dyes, xanthene dyes, indanthrene dyes, indigo dyes,thioindigo dyes, merocyanine dyes, thiazine dyes, acridine dyes andoxazine dyes, and they may be used singly or in the form of a mixture oftwo or more thereof. A mixing ratio of the dye to be used is in therange of about 0.1 to 30%.

In addition, when κ is small for the record and regenerative laserwavelength of the chelate compound of the dipyrromethene compoundrepresented by the general formula (1) with metal selected from therange of 520 to 690 nm, the recording layer may be mixed with a lightabsorbing compound having a maximum absorption in the wavelength rangeof 600 to 900 nm for the sake of the improvement of the recordcharacteristics and the like. Typical examples of the light absorbingcompound include cyanine dyes, squalirium dyes, naphthoquinone dyes,anthraquinone dyes, porphyrin dyes, tetrapyraporphirazine dyes,indophenol dyes, pyrylium dyes, thiopyrylium dyes, azulenium dyes,triphenylmethane dyes, xanthene dyes, indanthrene dyes, indigo dyes,thioindigo dyes, merocyanine dyes, thiazine dyes, acridine dyes, oxazinedyes, phthalocyanine dyes and naphthalocyanine dyes, and they may beused singly or in the form of a mixture of two or more thereof. A mixingratio of the dye to be used is in the range of about 0.1 to 30%.

Prior to the formation of the recording layer, the above-mentioned dyecan be mixed with any of a quencher, a dye decomposition accelerator, anultraviolet absorber, an adhesive and the like, or alternatively acompound having such an effect can also be introduced into the dye as asubstituent.

Typical examples of the quencher include metal complexes ofacetylacetonates, bisdithiols such as bisdithio-α-diketones andbisphenyldithiols, thiocatechols, salicylaldehydeoximes,thiobisphenolates and the like. In addition, amines are suitable.

Examples of the dye decomposition accelerator include metallic compoundssuch as metallic anti-knock agents, metallocene compounds and metalcomplexes of acetylacetonates.

Additionally, if necessary, a binder, a leveling agent and ananti-foaming agent can also be used together. Examples of the preferablebinder include polyvinyl alcohol, polyvinyl pyrrolidone, nitrocellulose,cellulose acetate, ketone resins, acrylic resins, polystyrene resins,urethane resins, polyvinyl butyral, polycarbonates and polyolefins.

Prior to the formation of the recording layer on the substrate, a layercomprising an inorganic substance and a polymer may be formed on thesubstrate in order to improve the solvent resistance and the reflectanceof the substrate as well as the record sensitivity.

Here, the content of the metal chelate of the dipyrromethene compoundrepresented by the general formula (1) in the recording layer is 30% ormore, preferably 60% or more. It is also preferred that the content issubstantially 100%.

Examples of a technique for forming the recording layer include coatingmethods such as spin-coating, spraying, casting and an immersion, asputtering process, a chemical vapor deposition method and a vacuumvapor deposition method, but the spin-coating method is preferablebecause of being simple and easy.

In the case that a coating technique such as the spin-coating method isused, there can be used a coating solution prepared by dissolving ordispersing the metal chelate of the dipyrromethene compound representedby the general formula (1) in a solvent so that the content of the metalchelate may be in the range of 1 to 40% by weight, preferably 3 to 30%by weight. In this case, it is preferable to select the solvent whichdoes not damage the substrate. Examples of the solvent include alcoholsolvents such as methanol, ethanol, isopropyl alcohol,octafluoropentanol, allyl alcohol, methyl cellosolve, ethyl cellosolveand tetrafluoropropanol, aliphatic and alicyclic hydrocarbon solventssuch as hexane, heptane, octane, decane, cyclohexane, methylcyclohexane,ethylcyclohexane and dimethylcyclohexane, aromatic hydrocarbon solventssuch as toluene, xylene and benzene, hydrocarbon halide solvents such ascarbon tetrachloride, chloroform, tetrachloroethane and dibromoethane,ether solvents such as diethyl ether, dibutyl ether, diisopropyl etherand dioxane, ketone solvents such as acetone and3-hydroxy-3-methyl-2-butanone, ester solvents such as ethyl acetate andmethyl lactate, and water. They may be used singly or in the form of amixture of two or more thereof.

If necessary, the dye for the recording layer can be dispersed in apolymeric thin film or the like.

In the case that the solvent which does not damage the substrate cannotbe selected, the sputtering process, the chemical vapor depositionmethod or the vacuum vapor deposition method is effective.

No particular restriction is put on the thickness of the recordinglayer, but it is preferably in the range of 50 to 300 nm. If thethickness of the recording layer is less than 50 nm, heat diffusion islarge, so that the record may not be done, or strain may occur on arecord signal and a signal amplitude may decrease. On the contrary, ifthe thickness of the dye layer is more than 300 nm, the reflectance maybecome insufficient and reproducing signal characteristics maydeteriorate.

Next, a reflective layer having a thickness of preferably 50 to 300 nmis formed on the recording layer. As a material for the reflectivelayer, substances having the sufficiently high reflectance at thewavelength of the regenerative light, for example, metals such as Au,Al, Ag, Cu, Ti, Cr, Ni, Pt, Ta, Cr and Pd can be used singly or in theform of an alloy thereof. Above all, Au, Al and Ag are suitable as thematerials for the reflective layer, because of having the highreflectance. As the material for the reflective layer, substances otherthan mentioned above can also be used, and examples of such substancesinclude metals and semimetals such as Mg, Se, Hf, V, Nb, Ru, W, Mn, Re,Fe, Co, Rh, Ir, Zn, Cd, Ga, In, Si, Ge, Te, Pb, Po, Sn and Bi. Thematerial containing Au as the main component is suitable, because therefractive layer having the high reflectance can easily be obtained.Here, the term "main component" means a component which is contained ina ratio of 50% or more. It is also possible that a multilayer preparedby alternately laminating a thin film having a low refractive index anda thin film having a high refractive index in which the films are madefrom materials other than the metals can also be used as the reflectivelayer.

Examples of a technique for forming the reflective layer include asputtering process, an ion plating method, a chemical vapor depositionmethod and a vacuum vapor deposition method. In addition, for theimprovement of properties such as reflectance, record characteristicsand adhesive properties, an intermediate layer or an adhesive layer of aknown inorganic or organic material can be formed on the substrate orunder the reflective layer.

Furthermore, no particular restriction is put on a material for theprotective layer on the reflective layer, so long as it can protect thereflective layer from an external force. Examples of the organicmaterial for the protective layer include thermoplastic resins,thermosetting resins, electron radiation curing resins and UW curingresins. Moreover, examples of the inorganic material for the protectivelayer include SiO₂, Si₃ N₄, MgF₂ and SnO₂. The thermoplastic resin orthe thermosetting resin can be dissolved in a suitable solvent, and theresulting coating solution is applied and then dried, whereby theprotective layer can be formed. The UV curing resin can directly be usedas it is, or it can be dissolved in a suitable solvent to prepare acoating solution, and this coating solution is applied and thenirradiated with UV light to cure it, whereby the protective layer can beformed. Examples of the usable UV curing resin include acrylate resinssuch as urethane acrylate, epoxy acrylate and polyester acrylate. Thesematerials may be used singly or in the state of a mixture thereof, andthis kind of resin may also be used in the form of a singly layer or amultilayer.

Examples of a technique for forming the protective layer include coatingmethods such as spin-coating and casting, a sputtering process and achemical vapor deposition method, as in the case of the formation of therecording layer, but above all, the spin-coating method is preferable.

The thickness of the protective layer is usually in the range of 0.1 to100 μm, but in the present invention, it is in the range of 3 to 30 μm,preferably 5 to 20 μm.

On the protective layer, a label or the like can further be printed.

In addition, there may be employed a means of laminating the protectivesheet or the substrate on the surface of the reflective layer, oranother means of laminating the two optical record media so that thereflective layers may come in contact with each other. For the purposeof protecting the surface or preventing the deposition of dust or thelike, an ultraviolet curing resin layer, an inorganic thin film or thelike may be formed on the mirror surface of the substrate.

No particular restriction is put on the laser having a wavelength of 520to 690 nm referred to in the present invention, and examples of such alaser include a dye laser capable of selecting the wavelength in thewide range of visible light, a helium neon laser having a wavelength of633 nm, a high-output semiconductor laser having a wavelength of about680, 650 or 635 nm which has been developed of late, and ahigh-frequency conversion YAG laser having a wavelength of 532 nm. Inthe present invention, the high-density record and reproduction ispossible at one wavelength or plural wavelengths selected from them.

Next, the present invention will be described in detail with referenceto examples, but the scope of the present invention should not belimited to these examples.

EXAMPLE 1

0.2 g of a compound (2-1) mentioned in Table 1 among metal chelate ofdipyrromethene compounds represented by formula (1) was dissolved in 10ml of dimethylcyclohexane to prepare a dye solution. As a substrate,there was used a disc made of a polycarbonate resin and having a spiralpre-groove (track pitch=0.8 μm) thereon, a diameter of 120 mm and athickness of 1.2 mm.

This substrate was spin-coated with the dye solution at a rotationalfrequency of 1500 rpm, and then dried at 70° C. for 3 hours to form arecording layer. With regard to this recording layer, its maximumabsorption was present at 505 nm, and its optical constant was such thatat 680 nm, n was 2.1 and κ was 0.04; at 650 nm, n was 2.2 and κ was0.05; and at 635 nm, n was 2.3 and κ was 0.07.

Next, Au was sputtered on this recording layer by the use of asputtering device (CDI-900) made by Bulzers Co., Ltd. to form areflective layer having a thickness of 100 nm. As a sputtering gas, anargon gas was used. Sputtering conditions were that a sputtering powerwas 2.5 kW and a sputtering pressure was 1.0×10⁻² Torr.

In addition, the reflective layer was spin-coated with an ultravioletcuring resin SD-17 (made by Dainippon Ink & Chemicals, Inc.), and thenirradiated with ultraviolet light to form a protective layer having athickness of 6 μm, thereby preparing an optical recording medium.

Furthermore, recording was carried out on the optical recording mediumat a linear velocity of 3.5 m/sec under a laser power of 8 mW by the useof an optical disc evaluation device (DDU-1000) equipped with asemiconductor laser head having a lens numerical aperture of 0.6 at awavelength of 635 nm and made by Pulstech Industry Co., Ltd. and an EFMencoder made by KENWOOD Co., Ltd. so that a shortest pit length might be0.44 μm. After the recording, signals were reproduced by the use of anevaluation device equipped with a red semiconductor laser head (lensnumerical aperture=0.6) of 650 nm and 635 nm to measure a reflectance,an error rate and a modulation amplitude. As a result, all of themeasured values were good.

Next, recording was done at a linear velocity of 1.4 m/sec under a laserpower of 10 mW by the use of the optical disc evaluation device(DDU-1000) equipped with the 680 nm semiconductor laser head and made byPulstech Industry Co., Ltd. and the EEM encoder made by KENWOOD Co.,Ltd. so that a shortest pit length might be 0.60 μm. Afterward, signalswere reproduced from the recorded medium by the use of the optical discevaluation device (DDU-1000) equipped with the red semiconductor laserhead of 680 nm, 650 and 635 nm to measure a reflectance, an error rateand a modulation amplitude. As a result, all of the measured values weregood.

As described above, the recording and the reproduction couldsuccessfully be carried out on this medium by a plurality of laserwavelengths.

In this connection, the error rate was measured by the use of a CDdecoder (DR3552) made by KENWOOD Co., Ltd., and the modulation amplitudewas calculated in accordance with the following equation: ##EQU1##

EXAMPLE 2

The same procedure as in Example 1 was conducted except that a disc madeof a polycarbonate resin and provided with a spiral pre-groove (trackpitch=0.8 μm) thereon and having a diameter of 120 mm and a thickness of0.6 mm was used as a substrate, thereby forming a recording layer and areflective layer thereon.

In addition, the reflective layer was spin-coated with an ultravioletcuring resin SD-301 (made by Dainippon Ink & Chemicals, Inc.), andanother disc substrate made by the polycarbonate resin and having adiameter of 120 mm and a thickness of 0.6 mm was then superposedthereon. Afterward, these layers were irradiated with ultraviolet lightto form a laminated optical recording medium.

Next, recording was carried out on the thus formed medium by the use ofan optical disc evaluation device (DDU-1000) made by Pulstech IndustryCo., Ltd. and an EFM encoder made by KENWOOD Co., Ltd. in the samemanner as in Example 1 except that the optical disc evaluation devicewas equipped with a semiconductor laser head of 635 nm corresponding toa thickness of 0.6 mm. After the recording, signals were reproduced bythe use of an evaluation device equipped with a red semiconductor laserhead of 650 nm and 635 nm to measure a reflectance, an error rate and amodulation amplitude. As a result, all of the measured values were good.

EXAMPLE 3

The same procedure as in Example 2 was conducted except that a disc madeof a polycarbonate resin and provided with a spiral pre-groove (trackpitch=1.2 μm) thereon and having a diameter of 120 mm and a thickness of0.6 mm was used as a substrate, thereby forming an optical recordingmedium.

Next, recording was carried out on the thus formed medium by the use ofan optical disc evaluation device (DDU-1000) made by Pulstech IndustryCo., Ltd. and an EF encoder made by KENWOOD Co., Ltd. in the same manneras in Example 1 except that the optical disc evaluation device wasequipped with a semiconductor laser head of 635 nm corresponding to athickness of 0.6 mm. After the recording, signals were reproduced by theuse of an evaluation device equipped with a red semiconductor laser headof 650 nm and 635 nm to measure a reflectance, an error rate and amodulation amplitude. As a result, all of the measured values were good.

EXAMPLE 4

The same procedure as in Example 2 was conducted except that a disc madeof a polycarbonate resin and provided with a spiral pre-groove (trackpitch=0.7 μm) thereon and having a diameter of 120 mm and a thickness of0.6 mm was used as a substrate, thereby forming an optical recordingmedium.

Next, recording was carried out on the thus formed medium by the use ofan optical disc evaluation device (DDU-1000) made by Pulstech IndustryCo., Ltd. and an EFM encoder made by KENWOOD Co., Ltd. in the samemanner as in Example 1 except that the optical disc evaluation devicewas equipped with a semiconductor laser head of 635 nm corresponding toa thickness of 0.6 mm. After the recording, signals were reproduced bythe use of an evaluation device equipped with a red semiconductor laserhead of 650 nm and 635 nm to measure a reflectance, an error rate and amodulation amplitude. As a result, all of the measured values were good.

EXAMPLE 5

The same procedure as in Example 2 was conducted except that adipyrromethene metal chelate compound (3-1) mentioned in Table 1 anddiacetone alcohol as a coating solvent were used and a disc made of apolycarbonate resin and provided with a spiral pre-groove (trackpitch=0.53 μm) thereon and having a diameter of 120 mm and a thicknessof 0.6 mm was used as a substrate, thereby forming an optical recordingmedium. With regard to this recording layer, its maximum absorption waspresent at 520 nm, and its optical constant was such that at 532 nm, nwas 2.4 and κ was 0.15.

Next, recording was carried out on the thus formed medium at a linearvelocity of 3.8 m/sec under a laser power of 7 mW by the use of anoptical disc evaluation device equipped with a YAG high-frequencyconversion laser head of 532 nm corresponding to a thickness of 0.6 mmand an EFM encoder made by KENWOOD Co., Ltd. After the recording,signals were reproduced by the use of the same evaluation device. As aresult, a reflectance was about 51%, an error rate was 7 cps, and amodulation amplitude was 0.65, and all of these values were good.

EXAMPLES 6 to 95

The same procedure as in Example 2 was conducted except thatdipyrromethene metal chelate compounds (2-2 to 2-23, 3-2 to 3-13, 4-1 to4-51, 5-1 to 5-37, 11-1 to 11-10, 12-1 to 12-10) mentioned in Table 1were used, thereby forming optical record media..

Next, recording was carried out on the thus formed medium in the samemanner as in Example 1 by the use of an optical disc evaluation deviceequipped with an evaluation device equipped with a semiconductor laserhead of 635 nm made by Pulstech Industry Co., Ltd. and an EF4 encodermade by KENWOOD Co., Ltd. After the recording, signals were reproducedby the use of an evaluation device equipped with a red semiconductorlaser head of 650 nm and 635 nm to measure a reflectance, an error rateand a modulation amplitude. As a result, all of the measured values weregood.

Comparative Example 1

The same procedure as in Example 2 was conducted except that adipyrromethene metal chelate compound (2-1) was replaced withpentamethinecyanine dye NK-29291,3,3,1',3',3'hexamethyl-2',2'-(4,5,4'5'-dibenzo)indodicarbocyanineperchlorate, made by Japanese Photosensitive Dye Laboratory!, therebyforming an optical recording medium. Next, recording was carried out onthe thus formed medium at a linear velocity of 3.5 m/sec under a laserpower of 7 mW in the same manner as in Example 1 by the use of anevaluation device (DDU-1000) equipped with a semiconductor laser head of635 nm made by Pulstech Industry Co., Ltd. and an EFM encoder made byKENWOOD Co., Ltd. After the recording, signals were reproduced by theuse of an evaluation device equipped with a red semiconductor laser headof 650 nm and 635 nm, and as a result, a reflectance was low, an errorrate was large, and a modulation amplitude was small. In addition, whenthe reproduction was carried out for a long period of time, the signalsdeteriorated.

Comparative Example 2

The same procedure as in Comparative Example 1 was conducted except thatNK-2929 was replaced with trimethinecyanine dye NK791,3,3,1',3',3'-hexamethyl-2',2'-indodicarbocyanine iodide, made byJapanese Photosensitive Dye Laboratory!, thereby forming an opticalrecording medium. Next, recording was carried out on the thus formedmedium at a linear velocity of 3.5 m/sec under a laser power of 7 mW inthe same manner as in Example 1 by the use of an evaluation device(DDU-1000) equipped with a semiconductor laser head of 635 nm made byPulstech Industry Co., Ltd. and an EFM encoder made by KENWOOD Co., Ltd.After the recording, signals were reproduced by the use of an evaluationdevice equipped with a red semiconductor laser head of 650 nm and 635nm, and as a result, a waveform was distorted, an error rate was large,and a modulation amplitude was small. In addition, when the reproductionwas carried out for a long period of time, the signals deteriorated.

Table 2 shows the optical constants of the recording layers, thereflectances, the error rates and the modulation amplitudes in the casethat the respective media were recorded at 635 nm and the reproductionwas then carried out at 650 and 635 nm in Examples 1 to 4 and 6 to 95 aswell as Comparative Examples 1 and 2.

                  TABLE 2-1                                                       ______________________________________                                               Example                                                                       1    2      3      4    6    7    8    9                               ______________________________________                                        Formula No.                                                                            2-1    2-1    2-1  2-1  2-2  2-3  2-4  2-5                           Maximum  505    505    505  505  510  520  514  520                           absorption                                                                    (nm)                                                                          Optical                                                                       constant                                                                      At 650 nm                                                                     n*.sup.1 2.2    2.2    2.2  2.2  2.0  2.1  2.1  2.0                           κ*.sup.2                                                                         0.05   0.05   0.05 0.05 0.06 0.06 0.06 0.07                          At 635 nm                                                                     n        2.3    2.3    2.3  2.3  2.3  2.3  2.5  2.4                           κ  0.07   0.07   0.07 0.07 0.08 0.09 0.10 0.11                          Reproduction properties of signals recorded at 635 nm                         Reproduction                                                                  at 650 nm                                                                     Reflectance                                                                            59     61     62   59   59   56   57   55                            (%)                                                                           Error rate                                                                             8      7      5    8    9    10   10   12                            (cps)                                                                         Modulation                                                                             0.67   0.70   0.74 0.65 0.64 0.63 0.65 0.63                          amplitude                                                                     Reproduction                                                                  at 635 nm                                                                     Reflectance                                                                            59     58     61   57   58   56   55   54                            (%)                                                                           Error rate                                                                             6      6      7    8    9    8    9    8                             (cps)                                                                         Modulation                                                                             0.76   0.78   0.76 0.66 0.66 0.64 0.66 0.65                          amplitude                                                                     ______________________________________                                         *.sup.1 n; Refractive index                                                   *.sup.2 κ; Extinction coefficient                                  

                  TABLE 2-2                                                       ______________________________________                                               Example                                                                       10   11     12     13   14   15   16   17                              ______________________________________                                        Formula No.                                                                            2-6    2-7    2-8  2-9  2-10 2-11 2-12 2-13                          Maximum  520    526    530  560  556  518  522  506                           absorption                                                                    (nm)                                                                          Optical                                                                       constant                                                                      At 650 nm                                                                     n*.sup.1 2.2    2.1    2.0  2.1  2.2  2.0  2.0  2.1                           κ*.sup.2                                                                         0.10   0.08   0.11 0.10 0.08 0.09 0.11 0.10                          At 635 nm                                                                     n        2.5    2.4    2.5  2.4  2.5  2.4  2.4  2.4                           κ  0.12   0.12   0.13 0.13 0.10 0.12 0.12 0.11                          Reproduction properties of signals recorded at 635 nm                         Reproduction                                                                  at 650 nm                                                                     Reflectance                                                                            54     53     52   51   52   53   51   53                            (%)                                                                           Error rate                                                                             9      9      10   9    9    10   9    9                             (cps)                                                                         Modulation                                                                             0.62   0.63   0.61 0.62 0.59 0.62 0.62 0.63                          amplitude                                                                     Reproduction                                                                  at 635 nm                                                                     Reflectance                                                                            57     59     60   55   56   57   58   55                            (%)                                                                           Error rate                                                                             8      7      5    10   9    8    9    10                            (cps)                                                                         Modulation                                                                             0.66   0.67   0.68 0.67 0.66 0.65 0.64 0.63                          amplitude                                                                     ______________________________________                                         *.sup.1 n; Refractive index                                                   *.sup.2 κ; Extinction coefficient                                  

                  TABLE 2-3                                                       ______________________________________                                               Example                                                                       18   19     20     21   22   23   24   25                              ______________________________________                                        Formula No.                                                                            3-9    3-10   3-11 3-12 3-13 3-14 3-15 3-16                          Maximum  532    525    532  550  553  550  555  535                           absorption                                                                    (nm)                                                                          Optical                                                                       constant                                                                      At 650 nm                                                                     n*.sup.1 2.1    2.2    2.1  2.2  2.1  2.1  2.2  2.0                           κ*.sup.2                                                                         0.09   0.09   0.11 0.10 0.07 0.10 0.11 0.08                          At 635 nm                                                                     n        2.6    2.5    2.4  2.4  2.5  2.6  2.4  2.5                           κ  0.11   0.11   0.11 0.12 0.10 0.12 0.13 0.10                          Reproduction properties of signals recorded at 635 nm                         Reproduction                                                                  at 650 nm                                                                     Reflectance                                                                            56     57     56   58   59   60   59   60                            (%)                                                                           Error rate                                                                             9      10     11   9    9    11   10   11                            (cps)                                                                         Modulation                                                                             0.63   0.61   0.60 0.67 0.68 0.67 0.66 0.65                          amplitude                                                                     Reproduction                                                                  at 635 nm                                                                     Reflectance                                                                            54     55     56   57   58   57   56   57                            (%)                                                                           Error rate                                                                             12     11     13   9    8    9    8    8                             (cps)                                                                         Modulation                                                                             0.63   0.62   0.64 0.72 0.70 0.71 0.69 0.69                          amplitude                                                                     ______________________________________                                         *.sup.1 n; Refractive index                                                   *.sup.2 κ; Extinction coefficient                                  

                  TABLE 2-4                                                       ______________________________________                                               Example                                                                       26   27     28     29   30   31   32   33                              ______________________________________                                        Formula No.                                                                            3-17   2-14   2-15 2-16 2-17 2-18 2-19 2-20                          Maximum  535    505    512  510  520  530  511  560                           absorption                                                                    (nm)                                                                          Optical                                                                       constant                                                                      At 650 nm                                                                     n*.sup.1 2.1    2.2    2.1  2.0  2.1  2.0  1.9  2.0                           κ*.sup.2                                                                         0.10   0.10   0.09 0.10 0.10 0.08 0.09 0.08                          At 635 nm                                                                     n        2.4    2.5    2.4  2.4  2.5  2.3  2.2  2.2                           κ  0.10   0.11   0.10 0.12 0.11 0.09 0.08 0.08                          Reproduction properties of signals recorded at 635 nm                         Reproduction                                                                  at 650 nm                                                                     Reflectance                                                                            60     59     61   58   59   52   53   57                            (%)                                                                           Error rate                                                                             9      8      7    9    8    10   1I   9                             (cps)                                                                         Modulation                                                                             0.67   0.68   0.68 0.66 0.66 0.68 0.67 0.66                          amplitude                                                                     Reproduction                                                                  at 635 nm                                                                     Reflectance                                                                            58     59     60   57   59   59   58   57                            (%)                                                                           Error rate                                                                             6      7      5    7    8    11   10   9                             (cps)                                                                         Modulation                                                                             0.70   0.71   0.69 0.68 0.68 0.64 0.62 0.63                          amplitude                                                                     ______________________________________                                         *.sup.1 n; Refractive index                                                   *.sup.2 κ; Extinction coefficient                                  

                  TABLE 2-5                                                       ______________________________________                                               Example                                                                       34   35     36     37   38   39   40   41                              ______________________________________                                        Formula No.                                                                            2-21   2-22   2-23 3-2  3-3  3-4  3-5  3-6                           Maximum  508    502    510  548  565  550  562  560                           absorption                                                                    (nm)                                                                          Optical                                                                       constant                                                                      At 650 nm                                                                     n*.sup.1 1.9    1.8    1.9  1.9  1.8  2.0  2.1  1.9                           κ*.sup.2                                                                         0.06   0.05   0.05 0.06 0.05 0.07 0.08 0.07                          At 635 nm                                                                     n        2.1    2.2    2.0  2.1  2.2  2.1  2.1  2.2                           κ  0.06   0.07   0.08 0.07 0.07 0.08 0.08 0.08                          Reproduction properties of signals recorded at 635 nm                         Reproduction                                                                  at 650 nm                                                                     Reflectance                                                                            52     53     50   49   54   52   51   50                            (%)                                                                           Error rate                                                                             11     10     10   9    9    8    10   10                            (cps)                                                                         Modulation                                                                             0.57   0.56   0.55 0.56 0.57 0.58 0.59 0.59                          amplitude                                                                     Reproduction                                                                  at 635 nm                                                                     Reflectance                                                                            50     49     51   52   53   54   54   52                            (%)                                                                           Error rate                                                                             10     10     9    9    10   9    11   10                            (cps)                                                                         Modulation                                                                             0.56   0.57   0.56 0.56 0.55 0.66 0.67 0.64                          amplitude                                                                     ______________________________________                                         *.sup.1 n; Refractive index                                                   *.sup.2 κ; Extinction coefficient                                  

                  TABLE 2-6                                                       ______________________________________                                               Example                                                                       42   43     44     45   46   47   48   49                              ______________________________________                                        Formula No.                                                                            3-7    3-8    12-1 11-1 11-2 11-3 11-4 11-5                          Maximum  530    528    580  576  585  592  580  580                           absorption                                                                    (nm)                                                                          Optical                                                                       constant                                                                      At 650 nm                                                                     n*.sup.1 2.1    2.2    2.2  2.1  2.1  2.2  2.0  2.0                           κ*.sup.2                                                                         0.05   0.06   0.04 0.06 0.07 0.05 0.06 0.06                          At 635 nm                                                                     n        2.2    2.1    2.3  2.5  2.6  2.4  2.4  2.4                           κ  0.07   0.08   0.06 0.10 0.12 0.13 0.10 0.10                          Reproduction properties of signals recorded at 635 nm                         Reproduction                                                                  at 650 nm                                                                     Reflectance                                                                            53     51     58   59   61   59   60   60                            (%)                                                                           Error rate                                                                             9      10     9    9    9    10   11   11                            (cps)                                                                         Modulation                                                                             0.63   0.61   0.67 0.68 0.67 0.66 0.65 0.65                          amplitude                                                                     Reproduction                                                                  at 635 nm                                                                     Reflectance                                                                            54     53     57   58   57   56   57   57                            (%)                                                                           Error rate                                                                             9      8      9    8    9    8    8    8                             (cps)                                                                         Modulation                                                                             0.66   0.64   0.72 0.70 0.71 0.69 0.69 0.69                          amplitude                                                                     ______________________________________                                         *.sup.1 n; Refractive index                                                   *.sup.2 κ; Extinction coefficient                                  

                  TABLE 2-7                                                       ______________________________________                                               Example                                                                       50   51     52     53   54   55   56   57                              ______________________________________                                        Formula No.                                                                            11-6   12-2   12-3 12-4 12-5 11-7 11-8 11-9                          Maximum  582    610    590  605  575  580  578  570                           absorption                                                                    (nm)                                                                          Optical                                                                       constant                                                                      At 650 nm                                                                     n*.sup.1 2.1    2.2    2.1  2.0  2.1  2.0  1.9  2.0                           κ*.sup.2                                                                         0.09   0.10   0.09 0.10 0.10 0.08 0.09 0.08                          At 635 nm                                                                     n        2.5    2.5    2.4  2.4  2.5  2.3  2.3  2.3                           κ  0.10   0.11   0.10 0.12 0.11 0.09 0.08 0.08                          Reproduction properties of signals recorded at 635 nm                         Reproduction                                                                  at 650 nm                                                                     Reflectance                                                                            60     59     61   58   59   58   59   58                            (%)                                                                           Error rate                                                                             9      8      7    9    8    10   10   9                             (cps)                                                                         Modulation                                                                             0.67   0.68   0.68 0.66 0.66 0.68 0.67 0.66                          amplitude                                                                     Reproduction                                                                  at 635 nm                                                                     Reflectance                                                                            59     60     60   58   59   59   58   57                            (%)                                                                           Error rate                                                                             6      7      5    7    8    11   10   9                             (cps)                                                                         Modulation                                                                             0.69   0.71   0.69 0.68 0.68 0.64 0.62 0.63                          amplitude                                                                     ______________________________________                                         *.sup.1 n; Refractive index                                                   *.sup.2 κ; Extinction coefficient                                  

                  TABLE 2-8                                                       ______________________________________                                               Example                                                                       58   59     60     61   62   63   64   65                              ______________________________________                                        Formula No.                                                                            11-10  12-6   12-7 12-8 12-9 12-10                                                                              4-1  4-2                           Maximum  580    600    604  596  600  610  552  555                           absorption                                                                    (nm)                                                                          Optical                                                                       constant                                                                      At 650 nm                                                                     n*.sup.1 2.0    1.9    2.0  1.9  2.0  2.0  2.1  2.2                           κ*.sup.2                                                                         0.06   0.05   0.05 0.06 0.05 0.07 0.04 0.04                          At 635 nm                                                                     n        2.1    2.2    2.2  2.1  2.2  2.1  2.3  2.3                           κ  0.06   0.07   0.08 0.07 0.07 0.08 0.06 0.06                          Reproduction properties of signals recorded at 635 nm                         Reproduction                                                                  at 650 nm                                                                     Reflectance                                                                            52     53     50   52   54   52   56   55                            (%)                                                                           Error rate                                                                             11     10     10   9    9    8    9    10                            (cps)                                                                         Modulation                                                                             0.57   0.56   0.55 0.56 0.57 0.58 0.63 0.61                          amplitude                                                                     Reproduction                                                                  at 635 nm                                                                     Reflectance                                                                            50     49     51   52   53   54   54   54                            (%)                                                                           Error rate                                                                             10     10     9    9    10   9    12   12                            (cps)                                                                         Modulation                                                                             0.56   0.57   0.56 0.56 0.55 0.66 0.63 0.64                          amplitude                                                                     ______________________________________                                         *.sup.1 n; Refractive index                                                   *.sup.2 κ; Extinction coefficient                                  

                  TABLE 2-9                                                       ______________________________________                                               Example                                                                       66   67     68     69   70   71   72   73                              ______________________________________                                        Formula No.                                                                            4-3    4-4    4-5  4-6  4-7  4-8  4-9  4-10                          Maximum  552    556    561  562  558  581  560  561                           absorption                                                                    (nm)                                                                          Optical                                                                       constant                                                                      At 650 nm                                                                     n*.sup.1 2.2    2.1    2.1  2.1  2.0  2.1  2.2  2.1                           κ*.sup.2                                                                         0.04   0.05   0.07 0.04 0.06 0.04 0.05 0.04                          At 635 nm                                                                     n        2.2    2.6    2.5  2.3  2.5  2.1  2.3  2.5                           κ  0.06   0.11   0.12 0.12 0.10 0.05 0.06 0.06                          Reproduction properties of signals recorded at 635 nm                         Reproduction                                                                  at 650 nm                                                                     Reflectance                                                                            60     58     60   61   59   55   57   55                            (%)                                                                           Error rate                                                                             9      9      8    10   10   9    10   10                            (cps)                                                                         Modulation                                                                             0.65   0.68   0.66 0.67 0.65 0.62 0.61 0.61                          amplitude                                                                     Reproduction                                                                  at 635 nm                                                                     Reflectance                                                                            56     58     58   56   56   56   55   55                            (%)                                                                           Error rate                                                                             10     10     9    8    9    12   11   13                            (cps)                                                                         Modulation                                                                             0.71   0.70   0.70 0.69 0.68 0.61 0.62 0.64                          amplitude                                                                     ______________________________________                                         *.sup.1 n; Refractive index                                                   *.sup.2 κ; Extinction coefficient                                  

                  TABLE 2-10                                                      ______________________________________                                               Example                                                                       74   75     76     77   78   79   80   81                              ______________________________________                                        Formula No.                                                                            4-11   4-12   4-13 4-14 4-15 4-47 4-48 4-51                          Maximum  567    570    570  568  566  565  568  580                           absorption                                                                    (nm)                                                                          Optical                                                                       constant                                                                      At 650 nm                                                                     n*.sup.1 2.2    2.0    2.3  2.2  2.0  2.3  2.2  2.3                           κ*.sup.2                                                                         0.03   0.06   0.06 0.05 0.05 0.06 0.05 0.05                          At 635 nm                                                                     n        2.3    2.7    2.6  2.4  2.6  2.6  2.4  2.6                           κ  0.05   0.10   0.12 0.12 0.11 0.12 0.12 0.11                          Reproduction properties of signals recorded at 635 nm                         Reproduction                                                                  at 650 nm                                                                     Reflectance                                                                            58     59     60   59   61   60   59   61                            (%)                                                                           Error rate                                                                             9      8      9    10   10   9    10   10                            (cps)                                                                         Modulation                                                                             0.65   0.69   0.67 0.65 0.64 0.67 0.65 0.64                          amplitude                                                                     Reproduction                                                                  at 635 nm                                                                     Reflectance                                                                            57     60     57   56   58   57   56   58                            (%)                                                                           Error rate                                                                             9      8      9    8    8    9    8    8                             (cps)                                                                         Modulation                                                                             0.71   0.69   0.71 0.67 0.69 0.71 0.67 0.69                          amplitude                                                                     ______________________________________                                         *.sup.1 n; Refractive index                                                   *.sup.2 κ; Extinction coefficient                                  

                  TABLE 2-11                                                      ______________________________________                                               Example                                                                       82   83     84     85   86   87   88   89                              ______________________________________                                        Formula No.                                                                            5-1    5-2    5-3  5-4  5-5  5-6  5-7  5-8                           Maximum  576    584    578  580  589  575  573  573                           absorption                                                                    (nm)                                                                          Optical                                                                       constant                                                                      At 650 nm                                                                     n*.sup.1 2.2    2.2    2.2  2.3  2.1  2.2  2.2  2.0                           κ*.sup.2                                                                         0.05   0.04   0.06 0.04 0.05 0.07 0.07 0.06                          At 635 nm                                                                     n        2.4    2.3    2.3  2.4  2.5  2.6  2.3  2.4                           κ  0.07   0.06   0.05 0.06 0.10 0.11 0.11 0.10                          Reproduction properties of signals recorded at 635 nm                         Reproduction                                                                  at 650 nm                                                                     Reflectance                                                                            57     57     56   60   59   61   61   60                            (%)                                                                           Error rate                                                                             9      11     11   10   9    8    8    11                            (cps)                                                                         Modulation                                                                             0.62   0.62   0.60 0.69 0.68 0.67 0.65 0.65                          amplitude                                                                     Reproduction                                                                  at 635 nm                                                                     Reflectance                                                                            53     55     58   55   58   60   56   58                            (%)                                                                           Error rate                                                                             9      11     13   9    10   9    8    6                             (cps)                                                                         Modulation                                                                             0.62   0.62   0.64 0.71 0.69 0.71 0.70 0.69                          amplitude                                                                     ______________________________________                                         *.sup.1 n; Refractive index                                                   *.sup.2 κ; Extinction coefficient                                  

                                      TABLE 2-12                                  __________________________________________________________________________                Example                                                                                         Comp.                                                                              Comp.                                                  90 91 92 93 94 95 Ex. 1                                                                              Ex. 2                                      __________________________________________________________________________    Formula No. 5-9                                                                              5-10                                                                             5-11                                                                             5-12                                                                             5-13                                                                             5-14                                                                             NK2929                                                                             NK79                                       Maximum absorption                                                                        575                                                                              573                                                                              579                                                                              577                                                                              579                                                                              576                                                                              640  550                                        (nm)                                                                          Optical constant                                                              At 650 nm                                                                     n*.sup.1    2.3                                                                              2.2                                                                              2.0                                                                              2.2                                                                              2.1                                                                              2.2                                                                              1.9  2.1                                        κ*.sup.2                                                                            0.05                                                                             0.04                                                                             0.06                                                                             0.04                                                                             0.05                                                                             0.07                                                                             1.35 0.08                                       At 635 nm                                                                     n           2.4                                                                              2.3                                                                              2.2                                                                              2.3                                                                              2.4                                                                              2.6                                                                              1.8  2.3                                        κ     0.05                                                                             0.06                                                                             0.06                                                                             0.05                                                                             0.11                                                                             0.06                                                                             1.30 0.10                                       Reproduction properties of signals recorded at 635 nm                         Reproduction at 650 nm                                                        Reflectance (%)                                                                           55 57 59 58 59 60 9    56                                         Error rate (cps)                                                                          8  9  11 10 9  8  3000 550                                        Modulation amplitude                                                                      0.63                                                                             0.64                                                                             0.60                                                                             0.66                                                                             0.68                                                                             0.65                                                                             0.13 0.35                                       Reproduction at 635 nm                                                        Reflectance (%)                                                                           52 55 54 57 60 57 9    60                                         Error rate (cps)                                                                          12 10 13 11 8  10 2500 350                                        Modulation amplitude                                                                      0.62                                                                             0.62                                                                             0.65                                                                             0.67                                                                             0.70                                                                             0.69                                                                             0.15 0.38                                       __________________________________________________________________________     *.sup.1 n; Refractive index                                                   *.sup.2 κ; Extinction coefficient                                  

EXAMPLE 96

4.8 g of 1-formyl-3-phenylisoindole and 2.3 g of 2,4-dimethylpyrrolewere dissolved in 500 ml of ethanol under nitrogen stream, and 4.1 g of47% hydrobromic acid was added dropwise thereto, followed by stirring ata reflux temperature for 2 hours. After the solution was cooled to roomtemperature, the precipitated crystals were collected by filtration, andthen washed with ethanol and water to obtain 6.5 g of a compoundrepresented by the following formula (1-a): ##STR146##

Next, 2.8 g of a compound represented by formula (1-a) was dissolved in600 ml of ethanol, and 1.8 g of cobalt acetate tetrahydrate was addedthereto, followed by stirring at a reflux temperature for 2 hours. Aftercooling, the precipitated is crystals were collected by filtration,washed with water, and then recrystallized from ethanol to obtain 0.8 gof a compound represented by formula (4-1): ##STR147##

From the following analytical results, it was confirmed that theobtained product was a desired compound.

Results of elemental analysis (C₄₂ H₃₄ N₄ Co)

    ______________________________________                                                C           H      N                                                  ______________________________________                                        Calcd. (%)                                                                              77.17         5.24   8.57                                           Found (%) 78.50         5.76   8.69                                           ______________________________________                                    

MS (m/e): 654 (M⁺)

The thus obtained compound showed a maximum absorption at 545 nm in achloroform solution, and had a gram extinction coefficient of 1.46×10⁵ml/g·cm.

EXAMPLE 97

5.5 g of 1-formyl-3-(4-methoxphenyl)isoindole and 2.3 g of2,4-dimethylpyrrole were dissolved in 500 ml of ethanol under nitrogenstream, and 4.2 g of 47% hydrobromic acid was added dropwise thereto,followed by stirring at a reflux temperature for 2 hours. After thesolution was cooled to room temperature, the precipitated crystals werecollected by filtration, and then washed with ethanol and water toobtain 6.4 g of a compound represented by the following formula (1-b):##STR148##

Next, 3.0 g of a compound represented by formula (1-b) was dissolved in700 ml of ethanol, and 2.0 g of cobalt acetate tetrahydrate was addedthereto, followed by stirring at a reflux temperature for 2 hours. Aftercooling, the precipitated crystals were collected by filtration, washedwith water, and then recrystallized from ethanol to obtain 1.1 g of acompound represented by formula (4-2): ##STR149##

From the following analytical results, it was confirmed that theobtained product was a desired compound.

Results of elemental analysis (C₄₄ H₃₈ N₄ Co)

    ______________________________________                                                C           H      N                                                  ______________________________________                                        Calcd. (%)                                                                              77.52         5.62   8.22                                           Found (%) 76.91         5.60   8.19                                           ______________________________________                                    

MS (m/e): 682 (M⁺)

The thus obtained compound showed a maximum absorption at 547 nm in achloroform solution, and had a gram extinction coefficient of 1.20×10⁵ml/g·cm.

EXAMPLE 98

2.8 g of a compound represented by formula (1-a) was dissolved in 500 mlof ethanol, and 1.5 g of zinc acetate was added thereto, followed bystirring at a reflux temperature for 2 hours. After cooling, theprecipitated crystals were collected by filtration, washed with water,and then recrystallized from ethanol to obtain 1.6 g of a compoundrepresented by the following formula (4-3): ##STR150##

From the following analytical results, it was confirmed that theobtained product was a desired compound.

Results of elemental analysis (C₄₂ H₃₄ N₄ Zn)

    ______________________________________                                                C           H      N                                                  ______________________________________                                        Calcd. (%)                                                                              76.42         5.19   8.49                                           Found (%) 76.58         5.59   8.71                                           ______________________________________                                    

MS (m/e): 660 (M⁺)

The thus obtained compound showed a maximum absorption at 545 nm in achloroform solution, and had a gram extinction coefficient of 2.01×10⁵ml/g·cm.

EXAMPLE 99

5.0 g of 1-formyl-3-(4-tert-butylphenylthio)isoindole and 1.7 g of2,4-dimethylpyrrole were dissolved in 500 ml of ethanol under nitrogenstream, and 3.1 g of 47% hydrobromic acid was added dropwise thereto,followed by stirring at a reflux temperature for 2 hours. After thesolution was cooled to room temperature, the precipitated crystals werecollected by filtration, and then washed with ethanol and water toobtain 3.9 g of a compound represented by the following formula (1-c):##STR151##

Next, 0.5 g of a compound represented by formula (1-c) was dissolved in150 ml of ethanol, and 0.3 g of cobalt acetate tetrahydrate was addedthereto, followed by stirring at a reflux temperature for 2 hours. Aftercooling, the precipitated crystals were collected by filtration, washedwith water, and then recrystallized from ethanol to obtain 0.4 g of acompound represented by formula (4-4): ##STR152##

From the following analytical results, it was confirmed is that theobtained product was a desired compound.

Results of elemental analysis (C₅₀ H₅₀ N₄ S₂ Co)

    ______________________________________                                                C           H      N                                                  ______________________________________                                        Calcd. (%)                                                                              72.35         6.07   6.75                                           Found (%) 71.16         6.06   6.59                                           ______________________________________                                    

MS (m/e): 830 (M+)

The thus obtained compound showed a maximum absorption at 550 nm in achloroform solution, and had a gram extinction coefficient of 1.24×10⁵ml/g·cm.

EXAMPLE 100

4.8 g of 1-formyl-3-phenylisoindole and 2.9 g of2,4-dimethyl-3-ethylpyrrole were dissolved in 600 ml of ethanol undernitrogen stream, and 4.1 g of 47% hydrobromic acid was added dropwisethereto, followed by stirring at a reflux temperature for 2 hours. Afterthe solution was cooled to room temperature, the precipitated crystalswere collected by filtration, and then washed with ethanol and water toobtain 6.8 g of a compound represented by the following formula (1-d):##STR153##

Next, 2.8 g of a compound represented by formula (1-d) was dissolved in700 ml of ethanol, and 1.9 g of cobalt acetate tetrahydrate was addedthereto, followed by stirring at areflux temperature for 2 hours. Aftercooling, the precipitated crystals were collected by filtration, washedwith water, and then recrystallized from ethanol to obtain 1.7 g of acompound represented by formula (4-5): ##STR154##

From the following analytical results, it was confirmed that theobtained product was a desired compound.

Results of elemental analysis (C₄₆ H₄₂ N₄ Co)

    ______________________________________                                                 C          H      N                                                  ______________________________________                                        Calcd. (%) 77.84        5.96   7.89                                           Found (%)  77.60        6.03   7.91                                           ______________________________________                                    

MS (m/e): 710 (M⁺)

The thus obtained compound showed a maximum absorption at 555 nm in achloroform solution, and had a gram extinction coefficient of 1.47×10⁵ml/g·cm.

EXAMPLE 101

2.8 g of a compound represented by formula (1-d) was dissolved in 700 mlof ethanol, and 1.4 g of zinc acetate was added thereto, followed bystirring at a reflux temperature for 2 hours. After cooling, theprecipitated crystals were collected by filtration, washed with water,and then recrystallized from ethanol to obtain 2.1 g of a compoundrepresented by the following formula (4-6): ##STR155##

From the following analytical results, it was confirmed that theobtained product was a desired compound.

Results of elemental analysis (C₄₆ H₄₂ N₄ Zn)

    ______________________________________                                                 C          H      N                                                  ______________________________________                                        Calcd. (%) 77.14        5.91   7.82                                           Found (%)  76.96        6.01   8.31                                           ______________________________________                                    

MS (m/e): 716 (M⁺)

The thus obtained compound showed a maximum absorption at 554 nm in achloroform solution, and had a gram extinction coefficient of 1.83×10⁵ml/g·cm.

EXAMPLE 102

0.9 g of a compound represented by formula (1-c) was dissolved in 200 mlof ethanol, and 0.4 g of zinc acetate was added thereto, followed bystirring at a reflux temperature for 2 hours. After cooling, theprecipitated crystals were collected by filtration, washed with water,and then recrystallized from ethanol to obtain 0.7 g of a compoundrepresented by the following formula (4-7): ##STR156##

From the following analytical results, it was confirmed that theobtained product was a desired compound.

Results of elemental analysis (C₅₀ H₅₀ N₄ S₂ Zn)

    ______________________________________                                                 C          H      N                                                  ______________________________________                                        Calcd. (%) 71.79        6.02   6.70                                           Found (%)  71.25        5.92   6.43                                           ______________________________________                                    

MS (m/e): 837 (M⁺)

The thus obtained compound showed a maximum absorption at 550 nm in achloroform solution, and had a gram extinction coefficient of 2.33×10⁵ml/g·cm.

EXAMPLE 103

2.0 g of a compound represented by formula (1-c) and 0.4 g of potassiumcyanide were dissolved in 300 ml of ethanol, followed by stirring at areflux temperature for 7 hours. After the solution was cooled to roomtemperature, 300 ml of water and 5 g of rhodefine were added, and theprecipitated crystals were collected by filtration, and then washed withwater. The thus filtered agglomerates were dissolved in 100 ml ofchloroform, and a chloroform solution containing 0.7 g of bromine wasadded dropwise at room temperature. After stirring at room temperaturefor 10 minutes, the solution was concentrated, and then purified throughcolumn chromatography (silica gel-methanol:chloroform=1:20) to obtain1.4 g of a compound represented by the following formula (1-e):##STR157##

Next, 1.0 g of a compound represented by formula (1-e) was dissolved in300 ml of ethanol, and 0.4 g of copper acetate was added thereto,followed by stirring at a reflux temperature for 2 hours. After cooling,the precipitated crystals were collected by filtration, washed withwater, and then recrystallized from ethanol to obtain 0.5 g of acompound represented by formula (4-8): ##STR158##

From the following analytical results, it was confirmed that theobtained product was a desired compound.

Results of elemental analysis (C₅₂ H₄₈ N₆ S₂ Cu)

    ______________________________________                                                C           H      N                                                  ______________________________________                                        Calcd.(%) 70.60         5.47   9.50                                           Found (%) 71.21         5.39   9.46                                           ______________________________________                                    

MS (m/e): 885 (M⁺)

The thus obtained compound showed a maximum absorption at 574 nm in achloroform solution, and had a gram extinction coefficient of 1.12×10⁵ml/g·cm.

EXAMPLE 104

2.0 g of a compound represented by formula (1-a) was dissolved in 50 mlof dichloromethane, and 1.4 g of N,N-diisopropylethylamine was addedthereto, followed by stirring at room temperature for 30 minutes.Afterward, 1.6 g of boron trifluoride ethyl ether complex was added,followed by stirring for 2 hours. After water washing, dichloromethanewas distilled off, and the solution was then purified through columnchromatography (silica gel-methanol:chloroform=1:20) to obtain 0.9 g ofa compound represented by the following formula (5-1): ##STR159##

From the following analytical results, it was confirmed that theobtained product was a desired compound.

Results of elemental analysis (C₂₁ H₁₇ N₂ BF₂)

    ______________________________________                                                C           H      N                                                  ______________________________________                                        Calcd.(%) 72.86         4.95   8.09                                           Found (%) 72.23         5.17   7.99                                           ______________________________________                                    

MS (m/e): 346 (M⁺)

The thus obtained compound showed a maximum absorption at 569 nm in achloroform solution, and had a gram extinction coefficient of 2.26×10⁵ml/g·cm.

EXAMPLE 105

2.0 g of a compound represented by formula (1-b) was dissolved in 50 mlof dichloromethane, and 1.4 g of N,N-diisopropylethylamine was addedthereto, followed by stirring at room temperature for 30 minutes.Afterward, 1.5 g of boron trifluoride ethyl ether complex was added,followed by stirring for 2 hours. After water washing, dichloromethanewas distilled off, and the solution was then purified through columnchromatography (silica gel-methanol:chloroform=1:20) to obtain 0.8 g ofa compound represented by the following formula ##STR160##

From the following analytical results, it was confirmed that theobtained product was a desired compound.

Results of elemental analysis (C₂₂ H₁₉ N₂ OBF₂)

    ______________________________________                                                C           H      N                                                  ______________________________________                                        Calcd. (%)                                                                              70.24         5.09   7.45                                           Found (%) 70.54         5.32   7.41                                           ______________________________________                                    

MS (m/e): 346 (M⁺)

The thus obtained compound showed a maximum absorption at 576 nm in achloroform solution, and had a gram extinction coefficient of 2.13×10⁵ml/g·cm.

What is claimed is:
 1. An optical recording medium having at least arecording layer and a reflective layer on a substrate, said recordinglayer containing a dipyrromethene metal chelate compound represented byformula (2): ##STR161## wherein R¹ to R⁷ are each independently ahydrogen atom, halogen atom, nitro group, cyano group, hydroxyl group,amino group, carboxyl group, sulfonic acid group, alkyl group having 1to 20 carbon atoms, halogenoalkyl group having 1 to 20 carbon atoms,alkoxy group having 1 to 20 carbon atoms, alkenyl group having 2 to 20carbon atoms, alkoxyalkyl group having 2 to 20 carbon atoms,alkoxyalkyoxy group having 2 to 20 carbon atoms, aryloxy group having 6to 20 carbon atoms, acyl group having 1 to 20 carbon atoms,alkoxycarbonyl group having 2 to 20 carbon atoms, alkylaminocarbonylgroup having 2 to 20 carbon atoms, dialkylaminocarbonyl group having 3to 20 carbon atoms, alkylcarbonylamino group having 2 to 20 carbonatoms, phenylcarbonylamino group having 7 to 20 carbon atoms,phenylaminocarbonyl group having 7 to 20 carbon atoms, phenoxycarbonylgroup having 7 to 20 carbon atoms, aralkyl group having 7 to 20 carbonatoms, aryl group having 6 to 20 carbon atoms, heteroaryl group having 5to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms,phenylthio group having 6 to 20 carbon atoms, alkenyloxycarbonyl grouphaving 3 to 20 carbon atoms, aralkyloxycarbonyl group having 8 to 20carbon atoms, alkoxycarbonylalkoxycarbonyl group having 4 to 20 carbonatoms, alkylcarbonylalkoxycarbonyl group having 4 to 20 carbon atoms,mono(hydroxyalkyl)aminocarbonyl group having 2 to 20 carbon atoms,di(hydroxyalkyl)aminocarbonyl group having 3 to 20 carbon atoms,mono(alkoxyalkyl)aminocarbonyl group having 3 to 20 carbon atoms ordi(alkyoxyalkyl)aminocarbonyl group having 5 to 20 carbon atoms; R² andR³ and/or R⁵ and R⁶ may bond to each other to form an aromatic ringfused to a pyrrole ring; and the fused aromatic rings formed by thesegroups may be the same or different and are represented by formula (a):##STR162## wherein R⁸ to R¹¹ are each independently a hydrogen atom,halogen atom, nitro group, cyano group, hydroxyl group, amino group,carboxyl group, sulfonic acid group, alkyl group having 1 to 20 carbonatoms, halogenoalkyl group having 1 to 20 carbon atoms, alkoxy grouphaving 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms,alkoxyalkyl group having 2 to 20 carbon atoms, alkoxyalkoxy group having2 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, acylgroup having 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20carbon atoms, alkylaminocarbonyl group having 2 to 20 carbon atoms,dialkylaminocarbonyl group having 3 to 20 carbon atoms,alkylcarbonylamino group having 2 to 20 carbon atoms,phenylcarbonylamino group having 7 to 20 carbon atoms,phenylaminocarbonylamino group having 7 to 20 carbon atoms,phenoxycarbonyl group having 7 to 20 carbon atoms, aralkyl group having7 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, heteroarylgroup having 5 to 20 carbon atoms, alkylthio group having 1 to 20 carbonatoms, phenylthio group having 1 to 20 carbon atoms, alkenyloxycarbonylgroup having 3 to 20 carbon atoms, aralkyloxycarbonyl group having 8 to20 carbon atoms, alkoxycarbonylalkoxycarbonyl group having 4 to 20carbon atoms, alkylcarbonylalkoxycarbonyl group having 4 to 20 carbonatoms, mono(hydroxyalkyl)aminocarbonyl group having 2 to 20 carbonatoms, di(hydroxyalkyl)aminocarbonyl group having 3 to 20 carbon atoms,mono(alkoxyalkyl)aminocarbonyl group having 3 to 20 carbon atoms ordi(alkoxyalkyl)aminoocarbonyl group having 5 to 20 carbon atoms; R¹⁰ andR¹¹ may bond to each other to form an aromatic ring; and M is atransition metal.
 2. The optical recording medium according to claim 1which is recordable and reproducible by a laser light selected from thewavelength range of 520 to 690 nm.
 3. The optical recording mediumaccording to claim 1 wherein, at a laser wavelength, a refractive indexof the recording layer is 1.8 or more, and an extinction coefficient ofthe recording layer is in the range of 0.04 to 0.40.
 4. The opticalrecording medium according to claim 1 wherein a reflectance of a laserlight selected from the wavelength range of 520 to 690 nm is 20% or moreas measured from the side of the substrate.
 5. An optical recordingmedium having at least a recording layer and a reflective layer on asubstrate, said recording layer containing a dipyrromethene metalchelate compound represented by formula (3): ##STR163## wherein R¹ to R⁷are each independently a hydrogen atom, halogen atom, nitro group, cyanogroup, hydroxyl group, amino group, carboxyl group, sulfonic acid group,alkyl group having 1 to 20 carbon atoms, halogenoalkyl group having 1 to20 carbon atoms, alkoxy group having 1 to 20 carbon atoms, alkenyl grouphaving 2 to 20 carbon atoms, alkoxyalkyl group having 2 to 20 carbonatoms, alkoxyalkoxy group having 2 to 20 carbon atoms, aryloxy grouphaving 6 to 20 carbon atoms, acyl group having 1 to 20 carbon atoms,alkoxycarbonyl group having 2 to 20 carbon atoms, alkylaminocarbonylgroup having 2 to 20 carbon atoms, dialkylaminocarbonyl group having 3to 20 carbon atoms, alkylcarbonylamino group having 2 to 20 carbonatoms, phenylcarbonylamino group having 7 to 20 carbon atoms,phenylaminocarbonyl group having 7 to 20 carbon atoms, phenoxycarbonylgroup having 7 to 20 carbon atoms, aralkyl group having 7 to 20 carbonatoms, aryl group having 6 to 20 carbon atoms, heteroaryl group having 5o 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms,phenylthio group having 6 to 20 carbon atoms, alkenyloxycarbonyl grouphaving 3 to 20 carbon atoms, aralkyloxycarbonyl group having 8 to 20carbon atoms, alkoxycarbonylalkoxycarbonyl group having 4 to 20 carbonatoms, alkylcarbonylalkoxycarbonyl group having 4 to 20 carbon atoms,mono(bydroxyalkyl)aminocarbonyl group having 2 to 20 carbon atoms,di(hydroxyalkyl)aminocarbonyl group having 3 to 20 carbon atoms,mono(alkoxyalkyl)aminocarbonyl group having 3 to 20 carbon atoms ordi(alkoxyalkyl)aminocarbonyl group having 5 to 20 carbon atoms; R² andR³ and/or R⁵ and R⁶ may bond to each other to form an aromatic ringfused to a pyrrole ring; and the fused aromatic rings formed by thesegroups may be the same or different and are represented by formula (a):##STR164## wherein R⁸ and R¹¹ are each independently a hydrogen atom,halogen atom, nitro group, cyano group, hydroxyl group, amino group,carboxyl group, sulfonic acid group, alkyl group having 1 to 20 carbonatoms, halogenoalkyl group having 1 to 20 carbon atoms, alkoxy grouphaving 1 to 20 carbon atoms, alkenyl group having 2 to 20 carbon atoms,alkoxyalkyl group having 2 to 20 carbon atoms, alkoxyalkoxy group 2 to20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, acyl grouphaving 1 to 20 carbon atoms, alkoxycarbonyl group having 2 to 20 carbonatoms, alkylaminocarbonyl group having 2 to 20 carbon atoms,dialkylaminocarbonyl group having 3 to 20 carbon atoms,alkylcarbonylamino group having 2 to 20 carbon atoms,phenylcarbonylamino group having 7 to 20 carbon atoms,phenylaminocarbonyl group having 7 to 20 carbon atoms, phenoxycarbonylgroup having 7 to 20 carbon atoms, aralkyl group having 7 to 20 carbonatoms, aryl group having 6 to 20 carbon atoms, heteroaryl group having 5to 20 carbon atoms, alkylthio group having 1 to 20 carbon atoms,phenylthio group having 6 to 20 carbon atoms, alkenyloxycarbonyl grouphaving 3 to 20 carbon atoms, aralkyloxycarbonyl group having 8 to 20carbon atoms, alkoxycarbonylalkoxycarbonyl group having 4 to 20 carbonatoms, alkylcarbonylalkoxycarbonyl group having 4 to 20 carbon atoms,mono(hydroxyalkyl)aminocarbonyl group having 2 to 20 carbon atoms,di(hydroxyalkyl)aminocarbonyl group having 3 to 20 carbon atoms,mono(alkoxyalkyl)aminocarbonyl group having 3 to 20 carbon atoms ordi(alkoxyalkyl)aminocarbonyl group having 5 to 20 carbon atoms; and R¹⁰and R¹¹ may bond to each other to form an aromatic ring.
 6. The opticalrecording medium according to claim 5 which is recordable andreproducible by a laser light selected from the wavelength range of 520to 690 nm.
 7. The optical recording medium according to claim 5 wherein,at a laser wavelength, a refractive index of the recording layer is 1.8or more, and an extinction coefficient of the recording layer is in therange of 0.04 to 0.40.
 8. The optical recording medium according toclaim 5 wherein a reflectance of a laser light selected from thewavelength range of 520 to 690 nm is 20% or more as measured from theside of the substrate.